applied

sciences
Review
A Review of Three-Dimensional Scanning Near-Field
Optical Microscopy (3D-SNOM) and Its Applications
in Nanoscale Light Management
Paul Bazylewski, Sabastine Ezugwu ID
and Giovanni Fanchini * ID

Department of Physics and Astronomy, University of Western Ontario, London , ON N6A3K7, Canada;
pbazylew@uwo.ca (P.B.); sezugwu@uwo.ca (S.E.)
* Correspondence: gfanchin@uwo.ca; Tel.: +1-519-661-2111

Received: 21 June 2017; Accepted: 14 July 2017; Published: 22 September 2017

Abstract: In this article, we present an overview of aperture and apertureless type scanning near-field
optical microscopy (SNOM) techniques that have been developed, with a focus on three-dimensional
(3D) SNOM methods. 3D SNOM has been undertaken to image the local distribution (within ~100 nm
of the surface) of the electromagnetic radiation scattered by random and deterministic arrays of
metal nanostructures or photonic crystal waveguides. Individual metal nanoparticles and metal
nanoparticle arrays exhibit unique effects under light illumination, including plasmon resonance
and waveguiding properties, which can be directly investigated using 3D-SNOM. In the second
part of this article, we will review a few applications in which 3D-SNOM has proven to be useful
for designing and understanding specific nano-optoelectronic structures. Examples include the
analysis of the nano-optical response phonetic crystal waveguides, aperture antennae and metal
nanoparticle arrays, as well as the design of plasmonic solar cells incorporating random arrays of
copper nanoparticles as an optical absorption enhancement layer, and the use of 3D-SNOM to probe
multiple components of the electric and magnetic near-fields without requiring specially designed
probe tips. A common denominator of these examples is the added value provided by 3D-SNOM in
predicting the properties-performance relationship of nanostructured systems.

Keywords: scanning near-field optical microscopy; c-SNOM; s-SNOM; nanoscale imaging;

nanoparticles; 3D SNOM

1. Introduction
Imaging of nanoscale features has been a long standing challenge in optical microscopy. In the
late 19th century an apparent fundamental limit on the maximum resolution of an optical image
was formulated based on the diffraction theory of light [1]. Although this formulation suggested
that optical microscopy was limited to micron-scale objects, the diffraction limit has since been
overcome through the development of super resolution techniques operating in the far-field [1–7].
Far-field super resolution strategies make use of enhanced contrast using a secondary process such
as fluorescence or scattering to image subwavelength nanostructures. Fluorescence imaging was
one of the first super resolution techniques to be developed. It utilizes fluorescence emitted from
a fluorophore used to mark a sample rather than diffracted light, allowing for nanoscale images to
be produced down to single-molecule resolution [2]. Fluorescence imaging forms the backbone of
super resolution techniques capable of nanoscale imaging, that includes stimulated emission depletion
(STED) microscopy, photo-activated localization microscopy, structured illumination spectroscopy,
and stochastic optical reconstruction microscopy (STORM) [2,6,7]. STED is a variation of fluorescence
imaging that achieves higher resolution by selectively quenching fluorophores used for labeling.
Through judicious choice of fluorophore and excitation laser, resolution in the tens of nanometers

Appl. Sci. 2017, 7, 973; doi:10.3390/app7100973 www.mdpi.com/journal/applsci

Appl. Sci. 2017, 7, 973 2 of 25

can be achieved [2]. STORM employs a variation of STED utilizing time-resolved selective switching
of fluorophores. Selective switching in this manner is used to collect a series of images that can be
combined to produce images with nanometer resolution. Through careful choice of measurement
optics, STORM can also be used to detect fluorescence from below a sample surface to construct
3D images [7]. The major drawback to any fluorescence based technique is the potential for photo
bleaching and sample damage brought on by the requirement for highly focused light sources.
Diffraction limited resolution can be avoided without the need for sample labeling, and the
dangers of photo bleaching though the use of scattering techniques such as optical coherence
tomography (OCT) which can achieve sub-micron resolution [3–5]. Researchers realized that OCT
could be enhanced with interferometry, which combines a series of images to produce an interference
pattern containing information about sub-wavelength surface features. OCT typically employs longer
wavelength light which has the added benefit of penetrating deeply into biological tissue. This gives
OCT the ability to collect 3D images at depths of hundreds of microns beneath a sample’s surface [4].
Light scattering techniques of this type are advantageous over fluorescence in that no labeling of
the samples are necessary, but at the cost of lower resolving power. Scanning near-field microscopy
(SNOM or NSOM) is the most recently developed super resolution technique based on light scattering
that is also capable of obtaining nanoscale images.
SNOM is a photon-in photon-out nano-optical imaging technique that uses near-field light to
construct nanoscale images. To make use of the near-field, a nanoscale probe is brought into the
near-field of a surface or object to be investigated, causing near-field evanescent waves to be scattered
into the far-field to be detected. Evanescent light experiences an exponential decay in the propagation
direction away from the originating surface that has the consequence of localizing the near-field to
a volume within ~100 nm nanometers of the originating emitter. This localization produces a high
intensity near-field very near the surface, which contains information about the surface properties
beyond the diffraction-limited maximum resolution of the far-field. In this way, SNOM can be used
to acquire super resolution optical images by scanning a probe tip over a surface in two dimensions,
or mapping the entire near-field of a surface by scanning in three dimensions.
Although SNOM is a nanoscale and contactless technique that does not require any fluorophore
labeling and is not subject to the issue of photo bleaching, it possesses other considerable challenges.
Probing the near-field of a surface makes it necessary to bring a nanoscale object within the near-field
of the surface. This requires finely machined tips that are most often coupled to an atomic force
microscope (AFM) system that allows three dimensional movement of the tip with nanometer
resolution. This requirement also makes SNOM primarily a surface technique compared to the
depth profiling possible with fluorescence labeling. The near-field light emitted from a sample is only
capable of propagating a short distance away from the emitting source, which minimizes the depth
profiling ability of SNOM.
This review article provides an overview of recent studies using the two different modes of SNOM,
aperture and apertureless, that have been applied for the characterization of thin films, nano particles,
and devices. The basic theory of SNOM, as well as the differences between the two basic SNOM modes,
apertureless and aperture-type, are presented in Section 2. Advances in aperture-type SNOM, defined
as mapping of electric and magnetic fields associated to scattering of electromagnetic radiation in the
near-field by a particle in the proximity of a nano-aperture are reviewed in Section 3. Imaging using
apertureless SNOM, defined as detection of electromagnetic radiation scattered by a particle by using
another particle (typically: a scanning probe tip) is presented in Section 4, along with how SNOM has
enabled mapping of otherwise inaccessible electromagnetic near-field properties. The final part of this
article, Section 5, reviews the use of SNOM in a three-dimensional scanning arrangement. Typically,
SNOM measurements are performed by raster scanning the SNOM tip in a two dimensional (x, y)
scan while carefully controlling the height of the tip above the surface. As an extension of this type of
scanning, 3D SNOM includes additional (x, y) scans moving the probe away from the surface in the
Appl. Sci. 2017, 7, 973 3 of 25

z-direction, and has been used to study light scattering near surfaces that is otherwise inaccessible by
other techniques.

2. Types of SNOM Methods

Any monochromatic light field can be represented by a vector field E(r) (similarly for the magnetic
component, H(r) containing components Am (r) and ϕm (r) that represent the spatially dependent
amplitude and phase of the vector components of the field (m = x, y, z in Cartesian coordinates).
The field can be represented by a set of waves of the form shown below.

+∞
Z
E (r ) = Ek eik·r dk (1)
−∞

where r represents spatial position, and each wave in the set is defined by its wavevector k and
complex amplitude Ek . For a given far-field distribution in a non-absorbingq
medium with real index
of refraction n, wavevector k is real with an amplitude defined by k o = k2x + k2y + k2z = 2πn/λ,
and wavelength in vacuum, λ. However, if k2x + k2y > k2o = ω 2 /c2 , then kz must have a non-zero
imaginary component. From Equation (1), any imaginary components within the far-field wavevector
k will result in an exponentially decaying amplitude. A light wave defined by such exponential decay is
termed an evanescent wave, and it experiences an exponential decay in amplitude moving away from
its originating location. The exponential decay in the propagation direction away from the originating
surface has the consequence of localizing the near-field to the originating emitter structure or interface
(within a distance less than 100 nm from the surface), which also results in the light field near a surface
being dominated by evanescent light [8]. A consequence of this is the real part of the wavevectors kn is
larger than ko , resulting in a near-field structure that contains information about the surface beyond
the diffraction-limited maximum resolution of the far-field.
Figure 1a illustrates the contrast between imaging in the far and near-fields; to make use of
near-field light the SNOM probe must be positioned within the near-field, close to the sample surface
at a distance r much less than the wavelength, λ, of the incident light. For this reason, SNOM is typically
demonstrated in practice coupled to a scanning microscopy system such as AFM. The cantilever system
of an AFM allows the SNOM tip to be positioned very close to the surface at a distance of tens of nm
(r << λ), to be within the near-field as shown in Figure 1a,b. The sample is then scanned in a raster
pattern to map the near-field distribution while maintaining a tip position very close to the surface.
Coupling to an AFM system also allows for simultaneous collection of a topography image and a
SNOM image, providing a method to map the surface nanoscale morphology directly to the optical
and chemical properties observed in the SNOM image.
Two distinct modes of SNOM imaging have been employed, and are classified by the type of tip
that is used. Aperture SNOM, also called collection SNOM (c-SNOM), uses hollowed out tips that
allow light to shine from the back out of, or up into, the tip as shown in Figure 1b. Aperture tips
function by generating near-field light by scattering of far-field light from the nanoscale aperture at the
end of the tip. The generated tip near-field is subsequently scattered off the sample surface, into the
far-field to be detected. Early versions of the SNOM technique employed a tapered optical fiber with a
metallic tip and a subwavelength opening for this purpose [1,8]. The standard aperture tip possesses a
circular opening with a typical diameter ranging from 80 to 250 nm, but can be as small as 10–20 nm
using advanced nanofabrication procedures. The particular size and shape of the tip and aperture, as
well as the tip composition dictate the range of frequencies that can be coupled to or scattered by the
sample. In this fashion designer tips have been fabricated with a desired aperture size and shape to
improve SNOM performance by increasing resolution, maximizing transmission [9,10], or providing
access to more exotic features such as magnetic near-fields using a bowtie, split ring, or pyramidal
(campanile) shape [10,11].
Appl. Sci. 2017, 7, 973 4 of 25
Appl. Sci. 2017, 7, 973 4 of 25

(a)

Figure 1.
Figure 1. The
The near-field
near-field and
and types
types ofof SNOM
SNOM tips. tips. (a)
(a) The
The far
far and
and near-field
near-field microscopy
microscopy arrangements
arrangements
are defined
are defined by by the
the proximity
proximity of of the
the probe
probe toto the
the nano
nano object
object being
being probed.
probed. When
When atat aa distance
distance (r)
(r) from
from
emitting object
the emitting objectthat
thatisismuch
muchlesslessthan
thanthethe wavelength
wavelength of of light
light used,
used, evanescent
evanescent light
light dominates
dominates the
the light
light field;
field; (b) Aperture
(b) Aperture SNOM SNOM wherewhere an evanescent
an evanescent lightlight
fieldfield created
created by aby a nanoscale
nanoscale opening
opening at
at the
the end of a tip is scattered off of the surface. Light scattered from the surface is detected
end of a tip is scattered off of the surface. Light scattered from the surface is detected in the far-field; in the far-
field;
(c) (c) Apertureless
Apertureless SNOM SNOM utilizes near-field
utilizes near-field lightfrom
light emitted emitted from the
the surface duesurface dueillumination
to external to external
illumination
that thatoff
is scattered is of
scattered
a sharpofftipof a sharp
into tip intotothe
the far-field befar-field
detected.to be detected.

Although there
Although thereare a large
are number
a large of applications
number that utilize
of applications that c-SNOM, some significant
utilize c-SNOM, limitations
some significant
of this technique
limitations remain;
of this (1) low
technique light transmission
remain; (1) low lightthrough the aperture,
transmission and the
through (2) aaperture,
fundamental
andlower
(2) a
limit of aperture size of approximately 10 nm due to the skin depth of metals [12].
fundamental lower limit of aperture size of approximately 10 nm due to the skin depth of metals [12].
Poor light
transmission through the tip aperture can be overcome through the use of high brightness light
Poor light transmission through the tip aperture can be overcome through the use of high brightness
sources such as lasers, while the lower limit on aperture size can be circumvented through the use of
light sources such as lasers, while the lower limit on aperture size can be circumvented through the use
apertureless tips. Apertureless-type SNOM systems, or scattering SNOM (s-SNOM), utilize light
of apertureless tips. Apertureless-type SNOM systems, or scattering SNOM (s-SNOM), utilize light
from an external source scattered from an apertureless tip which acts as an antenna to produce a
from an external source scattered from an apertureless tip which acts as an antenna to produce a source
source of evanescent light near the nanostructured sample surface as shown in Figure 1c.
of evanescent light near the nanostructured sample surface as shown in Figure 1c. Apertureless-type
Apertureless-type operation is advantageous in that it does not suffer from the fundamental size
operation is advantageous in that it does not suffer from the fundamental size limitations of c-SNOM,
limitations of c-SNOM, and can achieve resolution below 10 nm [1,8,13]. However, apertureless-type
and can achieve resolution below 10 nm [1,8,13]. However, apertureless-type SNOM systems are
SNOM systems are more challenging to implement than their aperture-type counterparts. This is due
more challenging to implement than their aperture-type counterparts. This is due to a relatively
to a relatively intense far-field background composed of light reflected or scattered directly from the
intense far-field background composed of light reflected or scattered directly from the sample surface.
sample surface. This unavoidably creates a large background signal over a spatial area much larger
This unavoidably creates a large background signal over a spatial area much larger than the near-field
than the near-field domain of the tip [14]. The background signal is additionally subject to artifacts if
domain of the tip [14]. The background signal is additionally subject to artifacts if the tip-sample
the tip-sample distance is not very carefully controlled, making correct interpretation of apertureless
distance is not very carefully controlled, making correct interpretation of apertureless SNOM images
SNOM images more difficult [15].
more difficult [15].

3. Aperture-Type SNOM

3.1. c-SNOM Spectroscopy

In aperture-type near-field microscopy, near-field radiation can be collected through the probe
tip where the size and shape of the aperture, as well as the composition of the tip can be tailored
towards the specific application over a wide range of wavelengths (200–1700 nm). This allows a host of
Appl. Sci. 2017, 7, 973 5 of 25

different spectroscopy techniques to be implemented alongside SNOM systems to allow spectroscopy

and imaging at sub-wavelength resolution. Techniques with which aperture-type SNOM has been
coupled include Fourier-transform infrared spectroscopy (FTIR) [8], fluorescence [16], and Raman
spectroscopy [17,18].
The lateral resolution of fluorescence from single molecules can be enhanced through near-field
imaging of strong fluorescent emitters. Fluorescence SNOM microscopy has been very successful as a
contrast method to enhance resolution using transmission, reflection, or phase contrast modes [19,20].
In Fluorescence microscopy, fluorophores such as engineered organic fluorescent molecules [21] or
fluorescent proteins [22] possessing different characteristic absorption and emission wavelengths are
used to label different parts of a sample. The ability to distinguish the contrast between fluorescent
signals in a given sample then depends on the type of optics and detector used to collect the image.
SNOM techniques have been employed as a natural extension of far-field microscopy to increase the
resolution, and c-SNOM has been employed in biological, thin film, and device imaging [23,24].
Aperture-type SNOM has also been applied with great success in Raman spectroscopy. Although
a review on SNOM Raman is beyond the scopes of this article, we cannot omit to report that
much research has been focused on increasing the Raman cross-section to the single molecule
detection limit. The sensitivity can be improved greatly by combining SNOM with other techniques
such as coherent anti-Stokes Raman scattering (CARS), stimulated Raman scattering [25], or tip
enhanced Raman scattering (TERS) [26]. More recently surface enhanced Raman scattering (SERS)
has demonstrated label-free single molecule resolution [18,27]. Coupling Raman spectroscopy with
c-SNOM systems overcomes the limitations of the other sensitivity enhancing techniques and can
achieve nanoscale-SNOM enhanced Raman spectroscopy [17]. Nano Raman is a c-SNOM technique
making use of aperture type tips placed within the near-field of a sample to be imaged. This technique
has been used to study inorganic crystals, polymer thin films, liquid-liquid interfaces at the nanoscale,
as well as mapping of single molecules on surfaces [17] an investigation that is not possible with
conventional far-field Raman.

3.2. Imaging Electrical and Magnetic Near-Fields

In addition to probing chemical and morphological properties, SNOM has shown the capability to
map electromagnetic near-fields in both c-SNOM and s-SNOM modes using careful tip design. Both the
amplitude and phase of the near-field can be mapped, with phase-sensitive c-SNOM measurements
allowing detection of the mode properties of light as it propagates through nanoscale waveguides
composed of nanoparticles or nanowires [28,29]. With these capabilities, construction of electric and
magnetic vector field maps in the near-field of exotic nanostructures, nanoparticles and nano-antennas
has been accomplished [8,30,31].
Several variations of electric and magnetic field mapping are available in the literature using
c-SNOM, including the ability to examine either the electric or magnetic near-field components
individually, or together to form the complete electromagnetic spectrum [29]. Direct mapping of
electric fields near sub wavelength holes acting as nanoantennas has been demonstrated using tips with
30 nm circular apertures [30,31]. Optical mapping of magnetic fields is more challenging, and was first
demonstrated using c-SNOM with a slit etched into the tip of an aperture probe [32]. Etching a slit in
the side of the probe in this way converts the aperture probe into split-ring resonator. This architecture
effectively converts the normally inaccessible out-of-plane component of the magnetic field (Hz ) into
detectable in-plane far-field radiation (Ex or Ey ). Careful probe design has also provided access to
the in-plane magnetic fields (Hx or Hy ), such as a pyramidal shaped probe that has been used to map
the magnetic response of plasmonic nanoantennas shown in Figure 2a [11,33]. Scanning electron
microscope (SEM) images of these plasmonic disk (320 nm) and ring (470 nm outer diameter, 300 nm
inner diameter) antennas are shown in the top row of Figure 2a. The antennas were excited by an Hy
magnetic dipole source, positioned 75 nm below the antennas, and SNOM imaging was used to reveal
the |Hy|2 near-field distribution near the antennas. The bottom row of Figure 2a shows experimental
Appl. Sci. 2017, 7, 973 6 of 25

electron microscope (SEM) images of these plasmonic disk (320 nm) and ring (470 nm outer diameter,
300 nm inner diameter) antennas are shown in the top row of Figure 2a. The antennas were excited
Appl. Sci. 2017, 7, 973 6 of 25
by an Hy magnetic dipole source, positioned 75 nm below the antennas, and SNOM imaging was used
to reveal the |Hy|2 near-field distribution near the antennas. The bottom row of Figure 2a shows
SNOM images
experimental for the
SNOM disk and
images ring
for the architectures.
disk The disk displays
and ring architectures. The diska dipole mode
displays which
a dipole modeproduces
which
a strong plasmon excitation due to the proximity of the probe, represented by a
produces a strong plasmon excitation due to the proximity of the probe, represented by a darkeneddarkened elliptical
spot. Forspot.
elliptical the ring, two
For the separated
ring, dark lobes
two separated darkare observed
lobes on opposite
are observed edges edges
on opposite of the of
ring.
theBoth
ring. cases
Both
correspond
cases well to
correspond thetosimulated
well field,field,
the simulated enabling directed
enabling design
directed of nanoantennas
design [33].[33].
of nanoantennas

(a) (b)

Figure 2.
Figure Electromagnetic near-fields
2. Electromagnetic near-fields probed
probed with
with c-SNOM.
c-SNOM. (a) (a) An
An example
example of
of magnetic
magnetic near-field
near-field
maps (H y ) of single nanostructures taken with a pyramid-probe c-SNOM, scale
maps (Hy) of single nanostructures taken with a pyramid-probe c-SNOM, scale bar is 300 nm bar is 300 nm[28].
[28].
(b) Measurements of the resonance shift of a photonic crystal nanocavity collected
(b) Measurements of the resonance shift of a photonic crystal nanocavity collected with a circular with a circular
aperture c-SNOM
aperture c-SNOM probeprobe (left).
(left). The
The distribution
distribution of
of the
the out-of-plane
out-of-plane component
component Hz
Hz of
of the
the unperturbed
unperturbed
cavity can be calculated from the resonance shift map (right). Reproduced with permission
cavity can be calculated from the resonance shift map (right). Reproduced with permission from from[8],
[8],
Copyright Nature Photonics,
Copyright Nature Photonics, 2014. 2014.

The realization that

The realization thatan anunspecialized
unspecialized aperture
aperture probeprobe
couldcould be sensitive
be sensitive to in-plane
to in-plane magneticmagnetic
fields
fields indicated
indicated thatmagnetic
that the the magnetic near-field
near-field couldcould be studied
be studied in in greater
greater detail.ItIthas
detail. hasbeen
been since shown
shown
that
that normal
normal circular
circular aperture
aperture c-SNOM
c-SNOM probes probes cancan in
infact
factbebesensitive
sensitiveto tomagnetic
magneticnear-fields
near-fields[29,34].
[29,34].
Through judicious choice of aperture size and metal coating thickness, thickness, SNOM
SNOM mapping
mapping of of H
Hxx, Hyy and
and
Ezz of
ofaaplane
planewave
wavehas hasbeen
beenthrough
through the themapping
mapping of of standing
standing wavewave patterns
patterns on on gold
gold films
films [29]. Using
Using
photonic crystal waveguides as aa test test environment,
environment, c-SNOM
c-SNOM imagesimages have
have shown
shown thatthat typical
typical circular
circular
aperture
aperture probes
probes areare roughly
roughly equally
equally sensitive
sensitive to to electric
electric and
and magnetic
magnetic fields,
fields, not
not just
just to
to the
the electric
electric
component
component [34].[34]. The
The left
left of
of Figure
Figure 2b 2b shows
shows thethe use
use ofof this
this technique
technique to to map
map thethe in-plane
in-plane mapmap of of the
the
resonance
resonance shift in in aa photonic
photonic crystal
crystal nanocavity,
nanocavity, which is made possible by the the shift
shift of
of the
thenanocavity
nanocavity
resonance
resonance whenwhenthe theapex
apex a normal
a normal circular
circular aperture,
aperture, metalmetal
coatedcoated
c-SNOM c-SNOM
probe isprobe
aboveisanabove
antinode an
antinode of the magnetic
of the magnetic field of thefield of the
cavity cavity
[29]. The[29].
rightThepartright part of2bFigure
of Figure shows2bthe shows the associated
associated out-
out-of-plane
of-plane
magneticmagnetic
component component of the
of the light light
field (Hfield (Hzcan
z ) that ) thatbecan be calculated
calculated for the forunperturbed
the unperturbed cavitycavity
[29].
[29].
TheseThese types
types of of electromagnetic
electromagnetic field maps field maps are
are crucially cruciallyin important
important the design and in the design and
characterization
characterization of nano scale
of nano scale optoelectronic optoelectronic
devices. A natural devices.
extension A natural extension onsothe
on the capabilities farcapabilities
demonstrated so far
for
demonstrated
c-SNOM is to map near-fields in three dimensions, which is discussed further in Section 5 where itin
for c-SNOM is to map near-fields in three dimensions, which is discussed further is
Section
used to 5examine
where ittheis used
threetodimensional
examine thelight threefield
dimensional
of photonic light field of
crystal photonic crystal waveguides.
waveguides.

4. Apertureless-Type SNOM
Imaging of electromagnetic near-fields has also been widely accomplished using non-aperture
SNOM tips (Figure 1c) which can obtain higher resolution images compared to c-SNOM.
The requirement for a precisely machined nano aperture is waived, but is replaced with other challenges
in terms of signal detection due to a large far-field background signal from an external light source.
Appl. Sci. 2017, 7, 973 7 of 25

Photonic crystal nanocavities are a suitable test environment with well-defined nanostructures that are
ideal to make use of the high resolution capabilities of s-SNOM probes [13,35–37]. Experiments
examining a mid-infrared inverse bowtie antenna using s-SNOM in a polarization-resolved
interferometric configuration have been used to reconstruct the near-field vector from the amplitude
and phase of the electric field components (Ex,y,z ) [36]. Tuning of high quality factor photonic
microcavities over a wide range of frequencies has been accomplished by introducing a subwavelength
dielectric tip [36,37]. These cavities enable the study of tip-sample interaction to advantageously
control their properties. This is made possible by varying the lateral and vertical position of the tip
near the cavity, which can be used to tune the resonator frequency while maintaining the cavity quality
factor [36].
The high resolution of s-SNOM that enables the study of microcavity resonators are also
ideal to examine near-field effects such as surface plasmons [38–41] in graphene and metal
nanostructures. Making use of IR light as the illumination source allows for collection of IR-SNOM
images [42,43], and may also be coupled to FTIR spectrometer to collect high resolution spectroscopy
measurements [38,44]. Imaging of plasmon effects and IR-coupled systems are discussed in the
next sections.

4.1. Surface Plasmon Imaging

Surface plasmon resonance is a phenomenon arising from the oscillation of free electrons near
a material surface under illumination by a light source. Surface plasmons may be localized (within
10’s of nanometers) on a surface due to nanostructures, or may propagate over larger areas depending
on the material properties. Using a suitable excitation source, imaging of a surface using s-SNOM
can reveal details about the surface plasmon distribution, as shown in Figure 3a for a wide piece
graphene ribbon on an SiC substrate, and Figure 3b for a graphene ribbon tapering to a point [33].
AFM images of the same flake before and after are shown on the leftmost and rightmost edges, and the
colored images show SNOM images taken with 9200 nm (left), 9681 nm (middle) and 10,152 nm (right)
light wavelengths. The plasmon resonance wavelength may be tuned over a wide spectral range by
adjusting the excitation wavelength used for s-SNOM in the IR spectrum. This is made possible by the
dependence of the dielectric constant of the SiC substrate on the excitation wavelength. In this way, the
propagation of plasmon waves over the graphene surface may be studied. In Figure 3a, fringes in the
wider part of the ribbon are due to plasmon interference caused by plasmon reflections at the graphene
edges. Examining the tapered ribbons shows interference fringes with a spacing that decreases with
increasing SiC dielectric constant. This is due to a larger substrate permittivity yielding a smaller
graphene plasmon wavelength [38]. This type of plasmon imaging can lead to improved s-SNOM
performance through the design of enhanced tips. A novel application that has been proposed using
graphene plasmonics is the fabrication of graphene-plasmon enhanced s-SNOM tips [39]. In this
unusual approach, localized plasmons on graphene are mingled with surface plasmon polaritons
to confine plasmon waves into the apex of a nearfield scanning optical microscopy tip. The tip is
fabricated as a traditional metallic s-SNOM tip coated with a layer of graphene, resulting in very low
loss, high resolution tips [39].
In addition to graphene, metal nanostructures have been investigated to study surface plasmon
polaritons (SPP). SPPs are a type of surface wave that can be guided along a surface with applications
in light generation or photonic data storage. This type of surface effect can be induced through the
introduction of cross grooves fabricated in an Au thin film [40]. SPP excitation is this case was found
to depend on the direction of the electric field of the incident light relative to the cross-sections of
the grooves [41]. s-SNOM is uniquely suited to study plasmon activity in nano structures such as
graphene because of the extremely high resolution and the requirement that the sample be illuminated
by a light field to produce plasmons.
Appl. Sci. 2017, 7, 973 8 of 25
Appl. Sci. 2017, 7, 973 8 of 25

(a)

(b)

Figure 3. S-SNOM images of graphene plasmons. (a) 1 mm wide graphene nano ribbons on an SiC
Figure 3. S-SNOM images of graphene plasmons. (a) 1 mm wide graphene nano ribbons on an SiC
substrate. The black and white images show AFM morphology, while the colored images were taken
substrate. The black and white images show AFM morphology, while the colored images were taken
with 9200 nm (left), 9681 nm (middle) and 10,152 nm (right) light wavelengths. The line plots on the
with 9200 nm (left), 9681 nm (middle) and 10,152 nm (right) light wavelengths. The line plots on the
panels at the far left and right edges represent the near-field images for λo = 9200 nm and λo = 10,152 nm;
panels at the far left and right edges represent the near-field images for λo = 9200 nm and λo = 10,152 nm;
(b) Tapered graphene ribbons on the same SiC substrate imaged with SNOM, where the arrows
(b) Tapered graphene ribbons on the same SiC substrate imaged with SNOM, where the arrows indicate
indicate localized resonant modes. Reproduced with permission from [38], Copyright Nature, 2012.
localized resonant modes. Reproduced with permission from [38], Copyright Nature, 2012.

4.2. Infrared Nano-Imaging

4.2. Infrared Nano-Imaging
Both infrared imaging and FTIR have been coupled to a SNOM system, and have been used
Both infrared imaging and FTIR have been coupled to a SNOM system, and have been used
successfully using s-SNOM [42–45]. In this arrangement, the sample is illuminated with far-field IR
successfully using s-SNOM [42–45]. In this arrangement, the sample is illuminated with far-field
light with the resulting near-field scattered from an s-SNOM tip. In order to collect FTIR spectra,
IR light with the resulting near-field scattered from an s-SNOM tip. In order to collect FTIR
the AFM-SNOM tip arrangement need not be modified; only additional detectors and optics are required.
spectra, the AFM-SNOM tip arrangement need not be modified; only additional detectors and
FTIR SNOM mapping has been used to great effect on other systems including biological systems,
optics are required. FTIR SNOM mapping has been used to great effect on other systems including
semiconductor devices or thin film stacks may be investigated with nano-FTIR systems [38,42–44].
biological systems, semiconductor devices or thin film stacks may be investigated with nano-FTIR
The high resolution of SNOM allows the structure of single proteins to be imaged [43], along with
systems [38,42–44]. The high resolution of SNOM allows the structure of single proteins to be
collection of a nano-FTIR of neighboring proteins.
imaged [43], along with collection of a nano-FTIR of neighboring proteins.
Access to sub-wavelength features of thin films can provide otherwise inaccessible information
Access to sub-wavelength features of thin films can provide otherwise inaccessible information
including polymorphism or phase coexistence in organic films. Figure 4a,b depict AFM and IR
including polymorphism or phase coexistence in organic films. Figure 4a,b depict AFM and IR
s-SNOM image of a pentacene thin film recorded using mid-infrared illumination, respectively [45].
s-SNOM image of a pentacene thin film recorded using mid-infrared illumination, respectively [45].
The topography image alone is not sufficient to identify two different phases of pentacene, thin film or
The topography image alone is not sufficient to identify two different phases of pentacene, thin film or
bulk phase, where the bulk phase is associated with larger grains and poor charge carrier mobility [45].
bulk phase, where the bulk phase is associated with larger grains and poor charge carrier mobility [45].
The corresponding IR s-SNOM image however, clearly identifies a mixed phase with larger ellipsoidal
The corresponding IR s-SNOM image however, clearly identifies a mixed phase with larger ellipsoidal
grains throughout the films. This is confirmed using nano-FTIR (Figure 4c) with peak fitting which
grains throughout the films. This is confirmed using nano-FTIR (Figure 4c) with peak fitting which
clearly identifies a shift in the resonance frequency of the bulk phase (green line, yellow ellipsoids in
clearly identifies a shift in the resonance frequency of the bulk phase (green line, yellow ellipsoids in
the image) compared to the surrounding thin film phase (blue line, red areas in the images).
the image) compared to the surrounding thin film phase (blue line, red areas in the images).
Appl. Sci. 2017, 7, 973 9 of 25
Appl. Sci. 2017, 7, 973 9 of 25

(a) (b)

(c)

Figure 4. S-SNOM IR and FTIR images. (a) AFM topography of a pentacene thin film; (b) the
Figure 4. S-SNOM
corresponding IR-SNOMIR and FTIR
image images.
excited with(a) AFM
907 cm−1topography
wavelength of a pentacene
light, scale bar isthin film;
2 μm; (c)(b) the
Nano-
corresponding IR-SNOM image excited with 907 cm −1 wavelength light, scale bar is 2 µm;
FTIR spectra taken at two different locations representing the thin film and bulk phases of a pentacene
(c) Nano-FTIR
film spectra
(40-nm thick) taken on
deposited at an
twoSiO different locations
2 substrate. representing
Lorentzian the thin
fits (curves) film
to the and
data bulkthat
reveal phases
the
of a pentacene
bulk filmline,
phase (green (40-nm thick)
yellow deposited
ellipsoids in on
thean SiO2 substrate.
image) displays aLorentzian fits (curves)
higher resonance to the than
frequency data
reveal
the that the bulk
surrounding thinphase (green(blue
film phase line, line,
yellow
redellipsoids
phase in inthethe image)Reproduced
images). displays a higher resonance
with permission
frequency than the surrounding thin film
from [45], Copyright Nature communications, 2014.phase (blue line, red phase in the images). Reproduced with
permission from [45], Copyright Nature communications, 2014.
5. Applications of 3D-SNOM
5. Applications of 3D-SNOM
Two-dimensional mapping of nanostructured surfaces at the sub-wavelength limit has been
slowlyTwo-dimensional mapping
maturing for decades, andofeventually
nanostructuredled tosurfaces at the sub-wavelength
many significant breakthroughslimit has been
including tip
slowly and
design maturing for to
coupling decades, and eventually
other systems such as IR led to many significant
spectroscopy. 3D light breakthroughs
mapping has byincluding
comparison tip
design and coupling to other systems such as IR spectroscopy. 3D light mapping
not been as greatly utilized. Early work in this field employed aperture tips composed of tapered has by comparison
not been
optical as greatly
fibers utilized.
to collect images Early work indistances
at variable this fieldfromemployed aperture
the surface tips composed
without the use of of tapered
advanced
optical fibers to collect images at variable distances from the surface without
AFM based force modulation [46,47]. In one case the researchers were able to detect Weiner fringes the use of advanced
AFM based
which are anforce modulation
interference [46,47].
pattern arisingIn one
fromcase the researchers
interference between were able to
incident anddetect Weiner
reflected fringes
light [46].
which
It was are an interference
found that the fringepattern
patternarising
can from interference
be collected between
through incident and
the nanoscale reflected
aperture of anlight [46].
optical
It was found that the fringe pattern can be collected through the nanoscale aperture
fiber, and can be used to reconstruct an image of the sample surface able to resolve features ~100 nm of an optical fiber,
and
in canAlternatively,
size. be used to reconstruct
images can anbeimage of the
collected insample
a planesurface
above aable to resolve
sample surfacefeatures
to image~100 nm inlight
scattered size.
Alternatively,
from images such
nanostructures can beascollected in a plane
a microgratings above
[47]. Thisawork
sample surface to image
demonstrated scattered
that SNOM light
can from
be used
nanostructures
to such as patterns
map light scattering a microgratings
arising [47].
fromThis work
devices indemonstrated
three dimensions that using
SNOM can beaperture
a nano used to tip.
map
light These
scattering
earlypatterns
studies arising from devices
lead to mapping in three
of light dimensions
and electric using ainnano
near-fields threeaperture
dimensionstip. that can
These early studies lead to mapping of light and electric near-fields in
provide unique insight for device applications where the spatial structure of plasmonic and magnetic three dimensions that
can provide
fields as wellunique insight
as forward for device
scattered light applications
fields can greatlywhere the spatial
affect structure of
device operation andplasmonic
performance. and
magnetic
In fields section,
the following as wellapplications
as forward of scattered
3D SNOM light fields can
compared greatly affect
to traditional device operation
2D scanning are discussed, and
performance. In the following section, applications of 3D SNOM compared
with examples of the use of 3D SNOM to study and improve the design of organic solar cells, to traditional 2D scanning
are discussed, with
nano-aperture examples
antennas, of the usearrays,
nanoparticle of 3D SNOM to study
and photonic and improve
crystal waveguidesthe design of organic solar
[28,29,34,48–52].
cells, nano-aperture antennas, nanoparticle arrays, and photonic crystal waveguides [28,29,34,48–52].
Figure 5 illustrates the equipment setup that can be used for 3D SNOM measurements.
This method employs a variation of collection mode where illumination is directed from the substrate
 Appl. Sci. 2017, 7, 973 10 of 25

Figure 5 illustrates the equipment setup that can be used for 3D SNOM measurements.
ThisSci.
Appl. method
2017, 7, employs
973 a variation of collection mode where illumination is directed from the substrate
10 of 25
side through an inverted microscope using a laser light source in the case transparent or nearly
transparent samples [48]. Alternatively the sample may illuminated from the surface side, but laser
side through an inverted microscope using a laser light source in the case transparent or nearly
illumination from the backside of the substrate has been found to greatly reduce the background of
transparent samples [48]. Alternatively the sample may illuminated from the surface side, but laser
scattered far-field light and improve the near-field signal intensity. A SNOM image in three
illumination from the backside of the substrate has been found to greatly reduce the background of
dimensions can be generated using a SNOM tip mounted on an AFM system and scanned in the
scattered far-field light and improve the near-field signal intensity. A SNOM image in three dimensions
near-field of the sample surface at variable distances z away from the surface. The tip is raster scanned
can be generated using a SNOM tip mounted on an AFM system and scanned in the near-field of the
over the sample surface in the x-y plane while moving at fixed intervals in the z-direction using a
sample surface at variable distances z away from the surface. The tip is raster scanned over the sample
piezoelectric scanner. Light is detected through an upright confocal optical microscope focused on
surface in the x-y plane while moving at fixed intervals in the z-direction using a piezoelectric scanner.
the aperture at the end of the tip for each point (x, y, z) in the scan. The intensity of scattered light
Light is detected through an upright confocal optical microscope focused on the aperture at the end of
collected by the tip aperture transmitted via optical fiber to be measured a photomultiplier tube.
the tip for each point (x, y, z) in the scan. The intensity of scattered light collected by the tip aperture
Using scans consisting of (x, y) slices in the z direction, the entire near-field and its boundary with the
transmitted via optical fiber to be measured a photomultiplier tube. Using scans consisting of (x, y)
far-field can be mapped.
slices in the z direction, the entire near-field and its boundary with the far-field can be mapped.

Figure5.5.Schematic
Figure Schematicofofcollection
collectionmode
mode operation
operation3D3DSNOM
SNOM system. (a)(a)
system. TheThepiezo-scanner
piezo-scanneris capable of
is capable
moving the tip in x, y and z directions to position the tip in any location in 3D space; (b) In the
of moving the tip in x, y and z directions to position the tip in any location in 3D space; (b) In the 3D 3D SNOM
configuration, SNOM and
SNOM configuration, topography
SNOM images can be
and topography simultaneously
images obtained from obtained
can be simultaneously AFM/SNOM from
scans of the x-y plane along the sample surface. Scanning along x-z
AFM/SNOM scans of the x-y plane along the sample surface. Scanning along x-z planes atbe
planes at a constant y can used to
a constant
obtain
y can abecross-section
used to obtainof light scattered byofnanostructures
a cross-section light scatteredat bydifferent heights from
nanostructures the sample
at different surface.
heights from
Reproduced with permission from [48], Copyright Nanoscale, 2015.
the sample surface. Reproduced with permission from [48], Copyright Nanoscale, 2015.

Theextent
The extentofofthethemapping
mappingcapabilities
capabilitiesdepends
dependson onthe
thespecific
specificarrangement
arrangementof ofaagiven
givenSNOM
SNOM
instrument.Table
instrument. Table11below
belowprovides
providesdetails
detailsofof3D
3DSNOM
SNOMmicroscope
microscopeconfigurations
configurationsthat thathave
havebeen
been
reportedininthe
reported theliterature
literature
inin terms
terms of of scanning
scanning range,
range, type
type of tip,
of tip, andand illumination
illumination source
source used.used.
FromFrom
the
the table
table SNOM SNOMimages images
can becan be collected
collected over volumes
over volumes that arethat are hundreds
hundreds of microns
of microns in size,
in size, with with a
a variety
ofvariety of illumination
illumination sources ranging
sources ranging from infrared
from infrared andlight
and visible visible lighttolasers
lasers directtothermal
direct thermal
heatingheating
of the
of and
tip the tip and sample.
sample.

Table1.1.Configuration
Table ConfigurationofofSNOM
SNOMinstruments
instrumentsreported
reportedininthe
theliterature.
literature.

z-Axis x-y Dimension Illumination

Author Year z-Axis x-y Dimension Illumination
Author Year Ref. Ref. Microscope Configuration
Microscope Configuration Scanned (μm
(µm2)) Wavelength
2
Scanned Wavelength
Umeda
Umeda 1992
1992 [46] [46] BentBent
metal, 100
metal, nm
100 nmaperture
aperture 30µm
30 μm 400
400 669nm
669 nm
Bacsa
Bacsa
2006
2006
[47] [47] Optical fiber , 0.3 μm aperture
Optical fiber , 0.3 µm aperture
2 μm
2 µm
99 780 nm
780 nm
Bek 2006 [13] Various apertureless 9 μm 120 670 nm
Bek 2006 [13] Various apertureless 9 µm 120 670 nm
Lalouat 2007 [37] 50 nm Cr-Au coated apertureless 50 nm 3 1.5 μm
50 nm Cr-Au coated
Lalouat
Burresi 2007
2009 [32] [37] Al coated,apertureless
100 nm aperture 50 nm †
fixed 83 1.5 µm
1.53 μm
Schnell 2010 [35] Si apertureless 30 nm 1.3 9.3 μm
Burresi 2009 [32] Al coated, 100 nm aperture fixed † 8 1.53 µm
Olmon 2010 [53] Pt coated 400 nm apertureless 200 nm 5 μm line scan 10.6 μm
Schnell 2010 [35] Si apertureless 30 nm 1.3 9.3 µm
Guo 2010 [51] Al coated 150 nm aperture microns 1 457 nm
Olmon 2010 [53] Pt coated 400 nm apertureless 200 nm 5 µm line scan 10.6 µm
Huth 2011 [43] FTIR, Au coated apertureless fixed † 5 μm line scan 10.7 μm
Guo 2010
Jones 2012 [44] [51] Al coated 150 nm aperture
FTIR, apertureless microns
10 μm 51 457 nm
thermal heating *
Huth 2011 [43] FTIR, Au coated apertureless fixed † 5 µm line scan 10.7 µm
Jones 2012 [44] FTIR, apertureless 10 µm 5 thermal heating *
Appl. Sci. 2017, 7, 973 11 of 25

Table 1. Cont.

z-Axis x-y Dimension Illumination

Author Year Ref. Microscope Configuration
Scanned (µm2 ) Wavelength
Rotenberg 2012 [31] 100 nm aperture fixed † 24 1.55 µm
Chen 2012 [38] Apertureless fixed † 4 9–10 µm
Bauld 2012 [54] 80 nm aperture 8 µm 50 532nm
Square hollow pyramid,
Costantini 2012 [55] microns 32 µm line scan 980 nm
100 nm aperture
Al coated pyramid,
Denkova 2013 [11] 30 nm 5 0.4–2 µm
100 nm aperture
Rotenberg 2013 [30] 100 nm aperture fixed † 800 1.55 µm
Kihm 2013 [34] 100 nm aperture 10 µm 100 780 nm
Amenabar 2013 [42] FTIR, Au coated apertureless fixed † 1.2 4–14 µm
le Feber 2014 [29] Al coated, 218 nm aperture 380 nm 1 1.57 µm
Al coated hollow pyramid,
Denkova 2014 [33] fixed † 1 0.4–2 µm
90 nm aperture
Westermeier 2014 [45] FTIR, apertureless fixed † 180 907 nm
Liu 2014 [56] Infrared, apertureless 0.4 µm 7.2 1.56 µm
Ouyang 2015 [28] 80 nm aperture 2 µm 4 532 nm
Ikeda 2015 [41] 20 nm apertureless 150 nm 1.5 633 nm
Ezugwu 2015 [48] 80 nm aperture 2 µm 2.5 532nm
Li 2015 [50] Si 10 nm apertureless 100 nm 0.15 633 nm
Square -based pyramid,
Martinez-Marrades 2016 [49] 2.7 µm 3.6 µm line scan 660 nm
100 nm aperture
Bulat 2016 [57] Optical fiber, 50 µm aperture fixed † 1600 532 nm
Klein 2017 [58] Au coated, 150 nm aperture 2 µm 10 663 nm
* Thermal heating of probe and stage. † Scans in the z-x or z-y planes were not performed.

5.1. 3D Probing of Near-Fields of Nanostructures

Surfaces composed entirely of metallic nanoparticles or composite films embedded with
nanoparticles may be incorporated in the architectures of optoelectronic devices to optimize their
performance. Nanoparticles can impart increased efficiency or functionality to traditional device
architectures if their implementation is well understood. 3D SNOM has been demonstrated to represent
an outstanding tool for a deeper understanding of similar systems, whereas other scanning probe
techniques are surface-sensitive only. Figure 6 summarizes the use of 3D SNOM to map plasmonic
waves and electric field enhancement. Gold nanoparticles embedded in a polyimide thin film were
investigated using SNOM equipped with an 80 nm aperture tip with illumination provided by 532 nm
laser light (Figure 6e) [54]. Gold nanoparticles are promising for use in nanoplasmonic devices because
they are strongly resistant to environmental oxidation, while displaying an appropriate plasmon
resonance suitable for harvesting light in the visible range. Gold nanoparticles nucleated within
the film layer with different annealing temperatures and atmospheres were visible in simultaneous
AFM (left side of Figure 6a–d) and c-SNOM (right side of the same) images. Comparison of AFM
and c-SNOM images for these transparent samples qualitatively indicates the different depth of
various nanoparticles within the film as on the surface detectable by AFM or below the surface
only detectable by SNOM. AFM indicates large (up to 2 µm) metallic microclusters near the surface
of the films, while smaller (<500 nm) nanoparticles are observed much deeper below the surface.
3D SNOM imaging scanning pattern in Figure 6e is used to image the plasmonic waves and electric
field enhancement at a distance z above the surface (Figure 6f). The mapping shows enhanced
light scattering intensity close to the surface of the films, with areas of constructive and destructive
interference evident moving away from the sample surface up to a distance of several microns.
Appl. Sci. 2017, 7, 973 12 of 25
Appl. Sci. 2017, 7, 973 12 of 25

Figure AFM (left)

Figure 6.6. AFM (left) and
and SNOM
SNOM (right)
(right) images
images of of Au
Au nanoparticles
nanoparticles embedded
embedded in in polyimide.
polyimide.
(a) ◦
(a) Annealing
Annealing at at 150
150 °CC in
in an
an oxygen
oxygen deficient
deficient environment
environment creates
creates large
large micron
micron sized
sized particles.
particles.
Identical samples annealed at (b) 250 ◦ C; and (c) 450 ◦ C show a decrease in nanoparticle size as the
Identical samples annealed at (b) 250 °C; and (c) 450 °C show a decrease in nanoparticle size as the
temperature ◦ C shows significantly
temperature isisincreased;
increased;(d) (d)Annealing
Annealingunder
underatmospheric
atmosphericconditions
conditionsat at250
250 °C shows significantly
different
differentmorphology
morphologyconsisting
consistingofofsmaller
smallerparticles
particles250
250nmnmin
insize;
size;(e)
(e)Schematic
Schematicof ofz-x
z-xc-SNOM
c-SNOMscans
scans
using
using an inverted configuration with laser illumination from beneath the substrate; (f) Near-fieldlight
an inverted configuration with laser illumination from beneath the substrate; (f) Near-field light
recorded moving away from the sample surface. Reproduced with permission from [54], Copyright
recorded moving away from the sample surface. Reproduced with permission from [54], Copyright
Applied Physics Letters, 2012.
Applied Physics Letters, 2012.

In
Inaddition
additionto togold
gold nanostructures,
nanostructures,semi semicontinuous
continuousfilmsfilmsof ofcopper
coppernanoparticles
nanoparticleshave havealso
alsobeen
been
identified as components for optoelectronic devices to manipulate scattered
identified as components for optoelectronic devices to manipulate scattered light fields and were light fields and were
studied
studiedby bymultidimensional
multidimensionalSNOM SNOMmethods.
methods. Small
Small metallic
metallic particles
particles of of appropriate
appropriateshapeshapeand andsize
size
can
can be
be used
used to to generate
generate large
largeplasmonic
plasmonic field
fieldenhancements
enhancements that that maymay be
be useful
useful for
foroptoelectronic
optoelectronic
devices
devices [59].
[59]. 3D3D spatial
spatial mapping
mapping of of these
these nanoparticles
nanoparticles in in the
the near-field
near-field revealed
revealed new
newphenomena
phenomena
concerning
concerninglight lightscattering
scatteringby by
nano-objects.
nano-objects. Radiation scattering
Radiation from nanostructures
scattering from nanostructures may have may several
have
potential applications
several potential in optoelectronic
applications devices: devices:
in optoelectronic in addition to providing
in addition information
to providing about theabout
information size,
shape, and
the size, location
shape, andof nanoparticles
location in a film, in
of nanoparticles 3Da SNOM
film, 3Dcan be used
SNOM cantobemap
usedscattered light fields
to map scattered in
light
space.
fields The properties,
in space. location, and
The properties, intensity
location, of scattered
and intensity light fields arelight
of scattered of paramount
fields areimportance
of paramount for
controlling
importancelight scattering inlight
for controlling optoelectronic
scattering devices such as solar
in optoelectronic cells,such
devices waveguides, and light
as solar cells, emitting
waveguides,
diodes.
and light3D SNOMdiodes.
emitting can be 3Dused to map
SNOM canconstructive
be used to map andconstructive
destructive and interference of scattered
destructive light
interference of
fields to help
scattered lightimprove
fields tothe design
help or optimize
improve the or
the design efficiency
optimize ofthe
such devices.of such devices.
efficiency
Figure
Figure 77 illustrates
illustrates how
how 3D 3D SNOM
SNOM mapping
mapping could
could be be combined
combined with with AFMAFM toto image
image arrays
arrays ofof
thermally
thermally nucleated
nucleated copper
copper nanoparticles
nanoparticles obtained
obtained using
using anan aperture
aperture tiptip [48].
[48]. The
The AFM
AFM image
image in in
shown
shown in in panel
panel (a) (a) was
was collected
collected simultaneously
simultaneously with with the
the SNOM
SNOM image image shown
shown in in panel
panel (b)(b) Yellow
Yellow
pixels in panel (b) represent the location of nanoparticles in panel (a) and show regions near the
nanoparticles of higher intensity forward-scattered light. Comparing the background signal to that
Appl. Sci. 2017, 7, 973 13 of 25

pixels
Appl. Sci.in2017,
panel (b) represent the location of nanoparticles in panel (a) and show regions near
7, 973 the
13 of 25
nanoparticles of higher intensity forward-scattered light. Comparing the background signal to that
of the
of the copper
copper nanoparticles
nanoparticles clearly
clearly indicates
indicatesthatthatvery
verynear
nearthe
thesample
samplesurface
surface(z(z≈ ≈0),0),
thethe
intensity
intensityof
light scattered by the bare glass substrate is significantly lower in intensity
of light scattered by the bare glass substrate is significantly lower in intensity compared to light compared to light
scattered from
scattered from the
the nanoparticles.
nanoparticles. From
From the the AFM
AFM image
image the
the nanoparticle
nanoparticle size
size is
is significantly
significantly smaller
smaller
than the illumination wavelength, λ = 532 nm, which means the scattered electric
than the illumination wavelength, λ = 532 nm, which means the scattered electric field produced by field produced by
the nanoparticles
the nanoparticles is is better
better represented
represented as as an
an infinite
infinite superposition
superposition of of multipoles
multipoles rather
rather than
than aa purely
purely
dipole field [48]. Such a multipolar field is expected to undergo a series of intensity
dipole field [48]. Such a multipolar field is expected to undergo a series of intensity oscillations moving oscillations
moving
away from awaythefrom the showing
surface surface showing
bands ofbandsmaxima of maxima and minima
and minima intervalinterval
distancesdistances z, a property
z, a property that is
thatdisplayed
not is not displayed by a purely
by a purely dipole
dipole field field [60].
[60].

Figure 7. (a) Topographic AFM and (b) c-SNOM images obtained simultaneously; (c) Light intensity
Figure 7. (x,
mapping (a) z)Topographic AFMthe
measured along andA–A’
(b) c-SNOM images
cross-section obtained
in panel (b,d)simultaneously; (c) Light profile
the integrated intensity intensity
in
mapping (x, z) measured along the A–A’ cross-section in panel (b,d) the integrated intensity
the z-direction along the A–A’ cross-section showing the positions of constructive (maxima) and profile
in the z-direction
destructive along
(minima) the A–A’ cross-section
interference of forward showing the positions
light scattered of constructive (maxima)
from Cu-nanoparticles in panel and
(c).
destructive (minima) interference of forward light scattered
Reproduced with permission from [48], Copyright Nanoscale, 2015. from Cu-nanoparticles in panel (c).
Reproduced with permission from [48], Copyright Nanoscale, 2015.

These oscillations are visible (Figure 7c) in an (x, z) c-SNOM scan of the line A–A’ shown in
These oscillations are visible (Figure 7c) in an (x, z) c-SNOM scan of the line A–A’ shown in
Figure 7b, confirming the multipolar nature of the near-field. The bands of oscillating intensity are
Figure 7b, confirming the multipolar nature of the near-field. The bands of oscillating intensity are
found to extend into the far-field up to distances of 5 µm away from the surface, and possess a
found to extend into the far-field up to distances of 5 μm away from the surface, and possess a nearly
nearly uniform intensity along the x-direction excepting a relatively lower intensity corresponding
uniform intensity along the x-direction excepting a relatively lower intensity corresponding to the
to the largest particles. This effect is observed because even on a surface where the nanoparticles
largest particles. This effect is observed because even on a surface where the nanoparticles are not
are not closely packed, they cannot be considered to be isolated when the inter-particle distances
closely packed, they cannot be considered to be isolated when the inter-particle distances remain
remain smaller than the wavelength of probing light. Variations in particle diameter were found to
smaller than the wavelength of probing light. Variations in particle diameter were found to affect the
affect the intensity of the first maximum of forward-scattered light as a function of average particle
intensity of the first maximum of forward-scattered light as a function of average particle size.
size. Light scattered from nanoparticles with larger diameters is coupled more closely to the surface,
Light scattered from nanoparticles with larger diameters is coupled more closely to the surface, which is
which is attributed to the dependence of the cross-section for near-field light absorption and scattering
attributed to the dependence of the cross-section for near-field light absorption and scattering on the
on the particle size [59]. As a consequence of this copper nanoparticles with a diameters of 80 nm
particle size [59]. As a consequence of this copper nanoparticles with a diameters of 80 nm or greater
or greater exhibit multipolar effects induced by Mie scattering that causes strong coupling of this
exhibit multipolar effects induced by Mie scattering that causes strong coupling of this scattered light
scattered light to the substrate in the nanoparticle vicinity.
to the substrate in the nanoparticle vicinity.
Figure 7d presents the integrated intensity of light scattered along the A–A’ cross-section labeled in
Figure 7d presents the integrated intensity of light scattered along the A–A′ cross-section labeled
Figure 7b and corresponding to the z-axis of Figure 7c. Maxima and minima arising from constructive
in Figure 7b and corresponding to the z-axis of Figure 7c. Maxima and minima arising from constructive
and destructive interference, respectively, are visible on the micron scale moving away from the surface.
and destructive interference, respectively, are visible on the micron scale moving away from the
For the nanoparticles specific to this sample the first intensity maximum of forward-scattered light is
surface. For the nanoparticles specific to this sample the first intensity maximum of forward-scattered
light is observed 1200 nm above the surface, within the far-field of scattered light. The absolute
maxima occurs further away in the far-field at Δz = 4400 nm. This information can be used to achieve
Appl. Sci. 2017, 7, 973 14 of 25

Appl. Sci. 2017, 7, 973 14 of 25

observed 1200 nm above the surface, within the far-field of scattered light. The absolute maxima occurs
further away
efficient in the far-field
light harvesting at ∆z =such
in devices 4400asnm. This
solar information
cells can be used
by incorporating to achieve
a layer efficient light
of nanoparticles into
harvesting in devices such as solar cells
their architecture at the appropriate location. by incorporating a layer of nanoparticles into their architecture
at the
Aappropriate
variation of location.
3D SNOM utilized stroboscopic measurements of different faces of the same film.
A variationhas
This technique of 3D
beenSNOM
used utilized
to great stroboscopic
effect to study measurements of different
symmetry breaking faces by
induced of theIR same
laser
film. This technique has been used to great effect to study symmetry breaking
illumination in a vanadium dioxide (VO2), thin film using IR s-SNOM. In strongly correlated electron induced by IR laser
illumination in a vanadium dioxide
materials, broken symmetries can result in (VO ), thin film using IR s-SNOM. In strongly correlated
2 separation of multiple phases in the course of a solid-solid electron
materials, broken symmetries can
phase transition, where VO2 exhibits such result in separation
a phaseoftransition
multiple phases in the courseclose
at a temperature of a solid-solid
to room
phase transition, where VO exhibits such a phase transition at a temperature
temperature (340 K) [56]. Figure 8 shows s-SNOM near-field images using an 18.8 mW near-IR
2 close to room temperature
pump
(340 K)
laser [56].atFigure
taken three 8different
shows s-SNOM
locationsnear-field
across the images
surfaceusing
of aan25018.8
nmmWVOnear-IR pump laser taken
2 film surface with their
at three different
corresponding locations
AFM images. across the surface
Elevating of a 250
the sample nm VO2 film
temperature to surface with their
334 K induces corresponding
a highly oriented
stripe state that presents a herringbone pattern with two distinct orientations representingstate
AFM images. Elevating the sample temperature to 334 K induces a highly oriented stripe the two that
presents a herringbone pattern with two distinct orientations
equivalent in-plane orientations of the monoclinic c-axis [56]. representing the two equivalent in-plane
orientations of the monoclinic c-axis [56].

Figure 8. AFM and SNOM images of a VO2 film undergoing 18.8 mW pump laser induced strain.
Figure 8. AFM and SNOM images of a VO2 film undergoing 18.8 mW pump laser induced strain.
The left side of (a–c) show SNOM (S3 ) images with AFM images on the right. The pump laser was
The left side of (a–c) show SNOM (S3) images with AFM images on the right. The pump laser was
switched off for 1 s between each scan. After each switch, patterns are formed due to a spontaneous
switched off for 1 s between each scan. After each switch, patterns are formed due to a spontaneous
structural symmetry breaking, with stripes aligning along two possible orientations of the monoclinic
structural symmetry breaking, with stripes aligning along two possible orientations of the monoclinic
c-axis shown by white lines. Reproduced with permission from [56], Copyright Applied Physics
c-axis shown by white lines. Reproduced with permission from [56], Copyright Applied Physics
Letters, 2014.
Letters, 2014.

These images
These images areare indicative
indicative of of aa spontaneous
spontaneous symmetry-breaking
symmetry-breaking phase phase separation
separation duedue toto
the blocking of the pump laser between measurements that varies the
the blocking of the pump laser between measurements that varies the temperature of the sample.temperature of the sample.
The re-illumination
The re-illuminationat at that
that start
startof
of each
each scan
scan produces
producesaa new new strained
strainedarchitecture
architecturein inthe
thefilm
film that
that is
is
similar but uniquely different from the previous state, and can be seem
similar but uniquely different from the previous state, and can be seem in both s-SNOM and AFM in both s-SNOM and AFM
images. The
images. Thesymmetry
symmetrybreaking
breakingin inthis
thisfilm
filmcan
canbe beunderstood
understoodconsidering
consideringaaLandau-like
Landau-likefree freeelastic
elastic
energymodel;
energy model;asasthe the material
material goes
goes through
through a transition
a transition to a distorted
to a distorted phasephase
of lowerof lower symmetry,
symmetry, long-
long-range elastic modes couple to allowed short-range modes to yield
range elastic modes couple to allowed short-range modes to yield two energy minima with equal two energy minima with
equal potentials and mirror symmetry, corresponding in this case to two
potentials and mirror symmetry, corresponding in this case to two different monoclinic c-axis different monoclinic c-axis
orientations with
orientations with mirror
mirror symmetry
symmetry [56].[56].
To gain additional insight
To gain additional insight into the into the structure
structure of of the
the films
films after
after aa phase
phase transition,
transition, s-SNOM
s-SNOM
measurementswere
measurements werealsoalsoconducted
conductedin inthe
thecross-sectional
cross-sectionalfacefaceofofthe
theVOVO22film,
film,asasshown
shownininFigure
Figure9.9.
These measurements were collected at a temperature 5 degrees below the
These measurements were collected at a temperature 5 degrees below the transition temperature, to transition temperature,
to produce
produce three
three adjacent
adjacent regions
regions areare shownwith
shown withcharacteristic
characteristicnear-field
near-fieldpatterns.
patterns.These
Theseimages
images can
can
be used
be used toto map
map the
the metal
metal nucleation
nucleation by by the
the property
property that
thataalarger
largers-SNOM
s-SNOMintensity
intensitycorresponds
correspondstotoa
a higher IR conductivity a greater metal density [56]. Although the nucleation pattern varies somewhat
across the film, within all the cross-section regions metallic nucleation occurs preferentially at the
film/substrate interface where the epitaxial strain is the strongest. These metallic regions can then
Appl. Sci. 2017, 7, 973 15 of 25

higher IR conductivity a greater metal density [56]. Although the nucleation pattern varies somewhat
Appl.
acrossSci. the
2017,film,
7, 973within
all the cross-section regions metallic nucleation occurs preferentially15atofthe 25

film/substrate interface where the epitaxial strain is the strongest. These metallic regions can then
extend
extend up
up to
to the
the VO
VO22film
filmsurface,
surface,where
whereaastripe
stripelike
likeherringbone
herringbonepattern
patternemerges
emergesseen
seenininFigure
Figure8.8.
Both cross-sectional and planar s-SNOM mapping enables a nanoscopic investigation of
Both cross-sectional and planar s-SNOM mapping enables a nanoscopic investigation of spontaneous spontaneous
symmetry
symmetry breaking
breakinginina a3D3Dgeometry.
geometry.This type
This of analysis
type can can
of analysis be extended to other
be extended materials,
to other and
materials,
illustrates a complimentary use of 3D SNOM to scan multiple faces of the same material.
and illustrates a complimentary use of 3D SNOM to scan multiple faces of the same material.

Figure 9.
Figure IRs-SNOM
9.IR s-SNOMimageimageofofthe
the cross-section
cross-section of of
thethe
VOVO 2 film
2 film at 335
at 335 K. The
K. The white
white lineslines represent
represent the
the boundary
boundary between
between crystal
crystal domains
domains as seen
as seen in in Figure
Figure 8. 8.
The The cross
cross sectionshows
section shows3 3distinct
distinctregions,
regions,
which indicate
which indicatethethenucleation
nucleationofofmetal
metalatoms
atomswhere
where a more
a more intense
intense IRIR s-SNOM
s-SNOM signal
signal corresponds
corresponds to
to a higher IR conductivity. The image indicates that metal nucleation happens
a higher IR conductivity. The image indicates that metal nucleation happens preferentially at thepreferentially at the
film/substrateinterface
film/substrate interfacewhere
wherethetheepitaxial
epitaxialstrain
strainisisstrongest.
strongest.Reproduced
Reproducedwith withpermission
permissionfromfrom[56],
[56],
Copyright Applied
Copyright Applied Physics
Physics Letters,
Letters, 2014.
2014.

5.2. Optimization
5.2. Optimization of
of Nano-Optical
Nano-Optical Devices
Devices
The first
The first use
use ofof 3D
3D SNOM
SNOM to to probe
probe aa scattered
scattered lightlight field
field of
of an optoelectronic
optoelectronic devicedevice was was
accomplished by means of a focusing waveguide grating coupler
accomplished by means of a focusing waveguide grating coupler (FWGC) as an experimental system (FWGC) as an experimental
system
[61]. This[61].
studyThiswasstudy was undertaken
undertaken to evaluate to evaluate
SNOM asSNOM as a complimentary
a complimentary tool to characterize
tool to characterize FWGCs,
FWGCs,
which which are
normally normally
difficultare
and difficult and time to
time consuming consuming
accuratelyto accurately
analyze, analyze,
requiring a fullrequiring a full
3D calculation
3Dpredict
to calculation to predict their
their waveguiding waveguiding
properties. properties.
The focal The focalbyspot
spot produced such produced
FWGCs is bynanoscale
such FWGCs is
is size
nanoscale
near is sizesurface,
the grating near the and grating surface,
therefore and be
can only therefore
imagedcan only
using be imaged using
non-diffraction non-diffraction
limited techniques.
limited
In techniques.
this case, SNOM In was this case, SNOM
capable was capable
of imaging the real of imaging theofreal
performance theperformance
FWGC by imaging of the FWGC
the spot by
imaging
at differenttheheights
spot at about
differenttheheights
sample,about the sample, to
for comparison foracomparison
much simpler to a2D muchBlochsimpler
wave 2D Bloch
analysis
wave analysis
which was ablewhich to fullywas able to fullythe
characterize characterize
FWGC [61]. theThis
FWGC [61].
initial This initial investigation
investigation showed the utility showed of
the utility of 3D SNOM beyond scanning the near-field very close to
3D SNOM beyond scanning the near-field very close to the surface, and how it can be used to study the surface, and how it can be
usedscattering
light to study light scattering
antennas antennas and waveguides.
and waveguides.
3D-SNOM has
3D-SNOM has since
since been
been used
used toto investigate
investigate resonant
resonant illumination
illumination of of nano
nano antennae
antennae consisting
consisting
of ordered
of ordered nano-holes
nano-holes as as shown
shown in in Figure 10a [49,55]. Nano Nano holehole antennas
antennas can can possess
possess interesting
interesting
optoelectronicproperties
optoelectronic propertiesused usedtotoscatter
scatterlight
lightinina acontrolled
controlled way.The
way. The nano
nano holehole antenna
antenna shownshown in
in Figure
Figure 10a 10a consists
consists of a of
40 anm40thick
nm thick
gold filmgoldperforated
film perforatedwith 17with
holes 17ofholes
150 nm of 150 nm in diameter
in diameter arrayed
arrayed
in in a line separated
a line separated by 20 nm by 20 nm
spaces andspaces and illuminated
illuminated with 660 nm with 660light
laser nm [49].
laser Panel
light [49]. Panelthe
(b) shows (b)
showsofthe
result a 2D result of aheterodyne
digital 2D digitalholography
heterodynescan holography
above thescan above
sample the sample
surface to image surface to image
scattered light.
scattered light.
Although DHHAlthough
is capableDHH of 3Disimaging
capablesimilar
of 3D imaging
to 3D SNOM,similarittois3D SNOM,technique
a far-field it is a far-field
and technique
therefore
andresulting
the thereforeimagethe resulting imagelimited.
is diffraction is diffraction
This can limited.
be seen This canthe
from be corresponding
seen from the corresponding
SNOM image
showing much higher resolution details of the nano holes. This nanostructure has also been investigated
in three dimensions to probe the light scattered above the nanoholes as shown in Figure 10c.
The uniform light intensity near the surface indicates coupling between the nano holes. The interference
Appl. Sci. 2017, 7, 973 16 of 25

SNOM image showing much higher resolution details of the nano holes. This nanostructure has also
been investigated in three dimensions to probe the light scattered above the nanoholes as shown in
Appl. Sci.10c.
Figure 2017,The
7, 973
uniform light intensity near the surface indicates coupling between the nano holes. 16 of 25
The interference pattern observed in the SNOM image is a consequence of light originating from the
pattern that
surface observed
is back in scattered
the SNOMfromimagetheistip
a consequence of light from
itself and reflected originating
the Aufrom the surface
surface that is back
to be collected by
scattered
the tip. from the tip itself and reflected from the Au surface to be collected by the tip.

Figure 10.
Figure 10. Resonant
Resonant illumination of nano
illumination hole antenna.
of nano (a) Nano hole
hole antenna. antenna
(a) Nano experimental
hole configuration;
antenna experimental
(b) 2D scan of(b)
configuration; the2Dnano
scanhole
of thesurface using
nano hole far-field
surface usingDHH imaging
far-field DHH and phaseand
imaging as well asas
phase c-SNOM;
well as
(c) Scattered
c-SNOM; light intensity
(c) Scattered light in a plane in
intensity perpendicular to the sample
a plane perpendicular surface.
to the sampleReproduced with permission
surface. Reproduced with
permission from [49], Copyright
from [49], Copyright Optics Communications,
Optics Communications, 2016. 2016.

Nano antennas
Nano antennas or or apertures
apertures with
with more
more exotic
exotic shapes
shapes such
such as
as thethebowtie
bowtie antenna
antenna [50,51]
[50,51]have
have
beensought
been soughtafter
after
forfor their
their lightlight scattering
scattering properties.
properties. BowtieBowtie
shapedshaped
antennasantennas are designed
are designed to produce to
produce enhanced electric fields in the aperture between the two bowtie halves.
enhanced electric fields in the aperture between the two bowtie halves. Figure 11 shows the optical Figure 11 shows the
optical amplitude
amplitude distribution
distribution in the
in the space space
above above aantenna
a bowtie bowtie of antenna
this type,of this
using type, using imaging.
s-SNOM s-SNOM
imaging.
This bowtie This bowtie
antenna was antenna was manufactured
manufactured using focused using focused
ion beam ion beam
milling milling
to produce an to produce
aperture with an
aperture with an outline of 150 nm and a gap size of 20 nm in a 60 nm gold film to [50].
an outline of 150 nm and a gap size of 20 nm in a 60 nm gold film to [50]. From Figure 11a, the electric From Figure 11a,
the) field
(E electric (Ez) field is concentrated
is concentrated alongofthe
along the edges theedges of the bowtie-shaped
bowtie-shaped aperture gap. aperture gap. Theofcurvature
The curvature the side
z
walls of the bowtie aperture gap allows the near-field to spread along the curvatures and reduceand
of the side walls of the bowtie aperture gap allows the near-field to spread along the curvatures its
reduceconfinement
spatial its spatial confinement
to the aperture.to the aperture.
From the 3DFrom
SNOM thescans
3D SNOM scans the
the near-field cannear-field
be seen tocan be seen
extend up
to20extend
to nm from up the
to film
20 nm fromatthe
surface, filmpoint
which surface, at which
it drops point
off sharply in itintensity.
drops offThesharply in intensity.
optical phase image
The optical phase image (Figure ◦11b) clearly identifies a 180° phase shift that
(Figure 11b) clearly identifies a 180 phase shift that is characteristic of bowtie apertures, and extends is characteristic of
bowtie apertures, and extends past the near-field
past the near-field boundary seen in the amplitude image [50,51].boundary seen in the amplitude image [50,51].
The 2D optical amplitude and phase in an x-y plane directly above the film surface corresponding
to z = 0 are constructed from the volume data and shown in Figure 11c,d. In Figure 11c, two separate
hot spots of the Ez field with FWHMs of 90 nm are clearly identified above the apex of each half of
the bowtie, with a minima in the field at the center corresponding to the gap of the bowtie aperture.
The phase shift seen in the x-z scan is reproduced at the bowtie antenna surface, showing that this
effect extends spatially in three dimensions. The full three-dimensional field can be reconstructed
from these scans; Figure 11e shows the intersection of the x-y, x-z, and y-z data planes.
Appl. Sci. 2017, 7, 973 17 of 25
Appl. Sci. 2017, 7, 973 17 of 25

Figure 11. 3D
Figure 11. 3D SNOM
SNOM amplitude
amplitude and
and phase
phase images
images ofof aa bowtie
bowtie antenna.
antenna. The
The amplitude
amplitude (a)
(a) and
and phase
phase
(b) an x-z
(b) images in an x-z plane showing a cross-section of the bowtie aperture. Panels (c) and (d) are
images in plane showing a cross-section of the bowtie aperture. Panels (c) and (d) are 2D
2D
amplitude
amplitude and and phase
phase images,
images, respectively,
respectively, sized
sized 400
400 nmnm × 100 nm
× 100 nm and
and taken
taken at
at the
the bowtie
bowtie antenna
antenna
surface, zz =
surface, 0; (e)
= 0; (e) Combined
Combined scans
scans showing
showing the
the 3D
3D light
light field
field of
of the
the antenna
antenna where
where the
the white
white scale
scale bar
bar
represents 50 nm. Reproduced with permission from [50], Copyright Optics
represents 50 nm. Reproduced with permission from [50], Copyright Optics Express, 2015.Express, 2015.

In addition
The 2D optical to nano
amplitudeantennae, photonic
and phase in ancrystal
x-y plane waveguides
directly above(PhCWs) possess
the film surface evanescent
corresponding wave
fields
to z = 0that
arehave been investigated
constructed from the volume in great detail
data andusing
shown SNOM
in Figureimaging.
11c,d.In Inthese
Figure devices,
11c, two 3Dseparate
SNOM
can spots
hot be utilized
of theto Ezexamine
field with theFWHMs
six components
of 90 nmof arethe electric
clearly and magnetic
identified above fields.
the apex Measurements
of each half of at
increasing
the bowtie,distances
with a minima z aboveinthe thecrystal
field atcan thebe usedcorresponding
center to differentiateto between
the gapparallel electricaperture.
of the bowtie (E‖) and
magnetic
The phase(H ‖) fields.
shift seen in In the
the x-z
x, yscan
plane of symmetry,
is reproduced at only transverse
the bowtie antenna components (Ex, Ey, Hthat
surface, showing z) of this
the
electromagnetic
effect extends spatiallyfield are non-zero
in three and have
dimensions. beenthree-dimensional
The full detected using SNOM field can[29]. However, asfrom
be reconstructed the
distance
these from
scans; the surface
Figure 11e shows increases the relative
the intersection amplitudes
of the x-y, x-z, andof the
y-zelectric and magnetic fields and
data planes.
theirIn spatial profiles
addition to nano changes. This photonic
antennae, divergence occurs
crystal because a (PhCWs)
waveguides given mode is composed
possess evanescent of many
wave
Bloch that
fields harmonics
have been in superposition,
investigated ineach greatofdetail
which experiences
using SNOM imaging.a different decaydevices,
In these in the z-direction,
3D SNOM
which
can be can be investigated
utilized to examineusing the six3Dcomponents
SNOM. of the electric and magnetic fields. Measurements
Figure 12distances
at increasing shows the resultthe
z above of 3D SNOM
crystal can investigations of a silicon
be used to differentiate PhCW parallel
between with 120electric
nm radius (Ek )
holesmagnetic
and separated (Hbyk ) 420
fields. nm Inspaces.
the x, This
y planestructure
of is
symmetry, illuminated
only by 1570
transverse nm light
components along (E the
x , E plane
y , H z ) of
waveguide, which
the electromagnetic is maintained
field are non-zero in and
the waveguide by the photonic
have been detected using SNOM bandgap of However,
[29]. the surrounding as the
holes, and
distance confined
from the surfaceto theincreases
bulk of the thesilicon
relativebyamplitudes
total internal reflection.
of the electric andThe magnetic
PhCW acts a waveguide
fields and their
to confine
spatial lightchanges.
profiles incident This on the edge of the
divergence silicon
occurs PhCWa between
because given mode twoisrows of periodic
composed of many holes that
Bloch
create a periodicity
harmonics in superposition,in the dielectric
each of which properties of the asilicon
experiences different resulting
decay in inthe
confinement
z-direction,ofwhich the lightcan
between
be the holes.
investigated using Each 3Dindividual
SNOM. small panel in Figure 12 is a 2D scan of a portion of the waveguide,
collected
Figureat a12height
showsabove the surface
the result of 3D given
SNOM byinvestigations
the scale on the of left of the PhCW
a silicon figure. with
Panels 120(c)nmandradius
(d) of
Figureseparated
holes 12 showbythe 420measured
nm spaces.light Thisfield above
structure the sampleby
is illuminated where
1570 nm Lx and
lightLalong
y represent
the plane separate
of the
detectors that
waveguide, whichare issetmaintained
to preferentially measure the
in the waveguide by Ethe
x or Ey fieldbandgap
photonic components of therespectively.
surroundingThe holes,Lx
signal
and presentstoa the
confined minimum
bulk ofalong the center
the silicon of the
by total waveguide
internal (arrowThe
reflection. at the
PhCWbottomactsofa panel
waveguidec) thatto is
similar light
confine to the calculated
incident on the Exedge
in panel
of thea silicon
as expected.
PhCW betweenHowever, twotherows
signal obtainedholes
of periodic from thatLy create
greatly a
resembles the
periodicity calculated
in the dielectric Hxproperties
field rather ofthan Ey as expected.
the silicon resulting These observations
in confinement of theindicate that the the
light between 3D
SNOMEach
holes. measurements
individual small abovepanel
the sample
in Figuresurface
12 is a actually
2D scan of measure
a portion a superposition
of the waveguide, of the E‖ andatHa‖
collected
fields. above
height Therefore, using agiven
the surface symmetrical
by the scale c-SNOM probe
on the left it isfigure.
of the possible to access
Panels (c) andall(d)components
of Figure 12of showthe
electromagnetic
the measured light spectrum
field above above thea sample
PhCW using where3D Lx SNOM
and Ly mapping. The individual
represent separate detectors components
that are setcan to
be further decoupled using Maxwell’s equations combined with additional constraints such as
symmetry in the sample or measurements with probes of different shapes [29].
Appl. Sci. 2017, 7, 973 18 of 25

preferentially measure the Ex or Ey field components respectively. The Lx signal presents a minimum
along the center of the waveguide (arrow at the bottom of panel c) that is similar to the calculated
Ex in panel a as expected. However, the signal obtained from Ly greatly resembles the calculated
Hx field rather than Ey as expected. These observations indicate that the 3D SNOM measurements
above the sample surface actually measure a superposition of the Ek and Hk fields. Therefore, using a
symmetrical c-SNOM probe it is possible to access all components of the electromagnetic spectrum
above a PhCW using 3D SNOM mapping. The individual components can be further decoupled
using Maxwell’s equations combined with additional constraints such as symmetry in the sample or
Appl. Sci. 2017, 7, 973 18 of 25
measurements with probes of different shapes [29].

Figure 12. 3D
Figure12. 3D SNOM
SNOMdetection
detectionof
ofEEand
andH Hfields
fieldssimultaneously.
simultaneously.(a,b)
(a,b)Calculated
Calculatedelectric
electricand
andmagnetic
magnetic
fields in x-y planes above the PhCW surface up to a distance of 380 nm. (c,d) Measured 3D SNOM data
fields in x-y planes above the PhCW surface up to a distance of 380 nm. (c,d) Measured 3D SNOM
(left) and data fitted to the calculated result (right). Lx and Ly represent two photodetectors arranged to
data (left) and data fitted to the calculated result (right). Lx and Ly represent two photodetectors
preferentially detect Ex and Ey fields, respectively. Reproduced with permission from [29], Copyright
arranged to preferentially detect Ex and Ey fields, respectively. Reproduced with permission from [29],
Nature Photonics, 2014.
Copyright Nature Photonics, 2014.

Beyond
Beyondthe thestudy
studyof ofpreviously
previouslyexiting
exitingwaveguide
waveguidearchitectures,
architectures,3D 3DSNOM
SNOMhas hasalso
alsobeen
beenusedused
to aid in the design of other types of devices such as organic bulk heterojunction
to aid in the design of other types of devices such as organic bulk heterojunction (BHJ) solar cells. (BHJ) solar cells.
The
Thedistribution
distributionof ofscattered
scatteredlight
lightresulting
resultingof offrom
fromaananostructured
nanostructuredsurfacesurfacecancanalso
alsobebeutilized
utilizedto to
enhance
enhancethe theperformance
performanceof ofBHJs.
BHJs.The
Theprospects
prospectsof ofthis
thisconcept
concepthave havebeen
beenexplored
exploredusing
usingaastructured
structured
plasmonic
plasmonicarchitecture
architecturesolar
solarcell
cellcontaining
containingaalayer layerof ofcopper
coppernanoparticles.
nanoparticles.The Thearchitecture
architectureisisshown
shown
in
inFigure
Figure 13c,e
13c,e where
where an an SiO placed as
SiO22 thin film is placed as aa spacer
spacer between
betweenthe thesolar
solarcell
cellactive
activelayer
layerandanda
alayer
layerofofcopper
coppernanoparticles
nanoparticles[48]. [48]. Figure
Figure 13a
13a illustrates
illustrates thethe integrated
integrated scattered
scattered light
light intensity
intensity in
in the
the
SiOSiO 2 modified
2 modified device
device compared
compared to to
a areference
referencecell. cell.AAregion
region of of forward-scattered light light exhibiting
exhibiting
constructive
constructiveinterference
interferenceisisrevealed
revealedfromfromzz==0–550
0–550nm nmabove
abovethe thenanoparticle
nanoparticlelayerlayerwhen
whenthe thespacer
spacer
isis present, as well as strong constructive interference at a greater distance
present, as well as strong constructive interference at a greater distance from the nanoparticle from the nanoparticle
layers.
layers. This enhancement
enhancement regionregionisisthetheresult
resultofofcoupling
couplingbetween
betweennormally
normally incident
incident plane
plane waves
waves on
on
thetheSiOSiO 2 surface
2 surface and
and wavestravelling
waves travellinglaterally,
laterally,parallel
parallelto to the
the surface. The superposition of of these
these
lateral
lateralandandnormal
normalcomponents
componentsleads leadsto toscattered
scatteredlightlightwith
withincreased
increasedintensity
intensitythat
thatisiscombined
combinedwith with
the
the normally
normally incident
incident light
light in
inconstructive
constructiveinterference.
interference. By By contrast,
contrast, when
when the
the spacer
spacer isis not
not used
used
destructive
destructiveinterference
interferenceisisobserved
observedin inaaband
band160 160nm nmfromfromthethesample
samplesurface.
surface.This
Thishashasthetheeffect
effectofof
considerably
considerably depleting
depleting thethe near-field
near-fieldin inthe
theregion
regionwherewherethe thesolar
solarcell
cellactive
activelayer
layerwould
wouldbe beplaced
placed
in
inaatypical
typicalarchitecture.
architecture.In Inthe
thespacer-enhanced
spacer-enhanced cell cell the
theamplified
amplifiedforward-scattering
forward-scattering field fieldisisideally
ideally
located
locatedto tofall
fallininthe
theactive
activesolar
solarcell
cellregion.
region.
Appl. Sci. 2017, 7, 973 19 of 25
Appl. Sci. 2017, 7, 973 19 of 25

Figure 13.
13. Intensity
Intensityprofiles of scattered
profiles light light
of scattered aboveabove
the copper nanoparticles
the copper are shown
nanoparticles areinshown
panel (a)
in
for two cases of (b) bare nanoparticles and (c) nanoparticles modified with an SiO
panel (a) for two cases of (b) bare nanoparticles and (c) nanoparticles modified with an SiO2 spacer.2 spacer. Intensity
enhancement
Intensity of scattered
enhancement of light is observed
scattered light iswhen the spacer
observed whenisthein spacer
place. These films are
is in place. subsequently
These films are
incorporated incorporated
subsequently into solar cellinto architectures of (d) the reference
solar cell architectures solar cellsolar
of (d) the reference containing bare copper
cell containing bare
nanoparticles
copper without awithout
nanoparticles spacer and (e) the enhanced
a spacer cellenhanced
and (e) the including acell
200including
nm SiO2 spacer.
a 200I–V
nmcharacteristics
SiO2 spacer.
of the
I–V solar cells with
characteristics of thea solar
Cu-nanoparticle plasmonic layerplasmonic
cells with a Cu-nanoparticle (f) without and
layer (f)(g) with and
without the SiO 2 spacer
(g) with the
SiO 2 spacer
between between
copper copper nanoparticles
nanoparticles and the ITO-P3HT/PCBM
and the ITO-P3HT/PCBM solar
solar cell cell layer.
active active layer. Reproduced
Reproduced with
with permission
permission fromfrom
[48], [48], Copyright
Copyright Nanoscale,
Nanoscale, 2015.2015.

The use
The useofofnanoparticle
nanoparticle layers to enhance
layers to enhancelight collection was examined
light collection in solar cells
was examined fabricated
in solar cells
with and without a SiO 2 spacer. Solar cell architectures of this type are shown schematically in
fabricated with and without a SiO2 spacer. Solar cell architectures of this type are shown
Figure 13d,e in
schematically consisting
Figure 13d,eof aconsisting
BHJ active of alayer
BHJ prepared
active layerfrom a mixture
prepared from aofmixture
regioregular poly-(3-
of regioregular
hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C 61-butyric acid methyl ester (PCBM) [48]. A layer
poly-(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61 -butyric acid methyl ester (PCBM) [48].
oflayer
A copper nanoparticles
of copper is incorporated
nanoparticles on toponoftop
is incorporated theofindium tin oxide
the indium electrodes
tin oxide in both
electrodes devices
in both to
devices
serve as a forward scattering layer, and I–V curves were collected under
to serve as a forward scattering layer, and I–V curves were collected under inert nitrogen atmosphereinert nitrogen atmosphere
as shown
as shown in in Figure
Figure 13f,g
13f,g for
for the
the reference
reference and and spacer-enhanced
spacer-enhanced solar solar cells,
cells, respectively. Although the
respectively. Although the
I–V characteristics of the two devices are very similar under no illumination,
I–V characteristics of the two devices are very similar under no illumination, a significantly larger a significantly larger
photocurrent was
photocurrent was extracted
extracted from from devices
devices containing
containing the the spacer,
spacer, more
more than
than twice
twice the
the value
value obtainable
obtainable
in the
in the unmodified reference cell.
unmodified reference cell. The
The increase
increase in in photocurrent alone is
photocurrent alone is sufficient to improve
sufficient to improve the the power
power
conversion efficiency (PCE) from η = 1.38% with no spacer present to
conversion efficiency (PCE) from η = 1.38% with no spacer present to η = 3.08% on average with η = 3.08% on average with the
the
spacer. The increased PCE is a result of increased intensity of light scattered
spacer. The increased PCE is a result of increased intensity of light scattered by the layer of copper by the layer of copper
nanoparticles into
nanoparticles into the
the active
active layer
layer ofof the
the solar
solar cell.
cell.
The light scattering properties of copper
The light scattering properties of copper nanoparticles nanoparticles havehave also
also been
been extended
extended to to evanescent
evanescent
waveguidetechnology.
waveguide technology.It hasIt has been been
shown shown recently
recently that arrays
that arrays of copper of nanoparticles
copper nanoparticles can be
can be thermally
thermally nucleated from a thin layer of copper deposited on few layer
nucleated from a thin layer of copper deposited on few layer graphene sheets [28]. Under controlledgraphene sheets [28]. Under
controlled conditions of annealing temperature and atmosphere, the nanoparticles
conditions of annealing temperature and atmosphere, the nanoparticles can be encouraged to form can be encouraged
to form ordered
ordered arrays witharrays with interesting
interesting optoelectronic
optoelectronic properties properties
[28]. Figure[28].14Figure 14 presents
presents scanningscanning
electron
electron microscopy (SEM) images of copper nanoparticle arrays nucleated
microscopy (SEM) images of copper nanoparticle arrays nucleated on graphene flakes at different on graphene flakes at
different annealing
annealing temperatures.
temperatures. Superlattices Superlattices of copper nanoparticles
of copper nanoparticles are found toare found to
be formed at be formed at
intermediate
intermediate
annealing annealing(~350
temperatures temperatures
◦ C) where(~350 °C) where
nanoparticles nanoparticles
nucleate nucleate
preferentially alongpreferentially
graphene armchair along
edges. At the extremes, nucleation is either limited by low temperature, or promotes the appearance or
graphene armchair edges. At the extremes, nucleation is either limited by low temperature, of
promotes the
disordered appearance
arrays at higher oftemperatures.
disordered arrays at higher temperatures.
Appl.
Appl. Sci. 7, 973
2017, 7,
Sci. 2017, 973 20
20 of
of 25
25

Figure SEMimages
14. SEM
Figure 14. imagesofofcopper
coppernanoparticle
nanoparticle decorated
decorated graphene
graphene thin
thin films
films annealed
annealed for 8for 8 h at
hours at
(a) 200 ◦ C (b) 360 ◦ C, (c) 440 ◦ C. (d) At lower temperatures copper nanoparticles are formed in an
(a) 200 °C (b) 360 °C, (c) 440 °C. (d) At lower temperatures copper nanoparticles are formed in an
uneven
uneven layer,
layer, which
which are
are formed
formed which
which transitions
transitions to
to assemblies
assemblies of
of particles
particles that
that become
become spatially
spatially
separated at the highest temperature. Superlattices formed of lines of nanoparticles are formed
separated at the highest temperature. Superlattices formed of lines of nanoparticles are formed at the at
the intermediate temperature of 360 ◦ C. Reproduced with permission from [28], Copyright RSC
intermediate temperature of) 360 °C. Reproduced with permission from [28], Copyright RSC
Advances, 2015.
Advances, 2015.

C-SNOM
C-SNOM (x, (x, z)z)scans
scanswerewereused
usedtotocharacterize
characterize thethe
copper
coppernanoparticle
nanoparticle arrays andand
arrays determine the
determine
electric fieldfield
the electric intensity perpendicular
intensity perpendicularto thetoplane of theof
the plane substrate duringduring
the substrate excitation by a laser
excitation by source.
a laser
Figure
source.15f,g schematically
Figure show howshow
15f,g schematically the laser
howlight
the is applied
laser lighttoisthe coppertonanoparticle
applied the copper superlattices,
nanoparticle
where an ordered
superlattices, where lattice can exhibit
an ordered waveguiding
lattice can exhibitproperties.
waveguiding Modes are generated
properties. Modes byare
thegenerated
laser source,
by
with an evanescent
the laser source, with near-field propagating
an evanescent alongpropagating
near-field the sample surface
along the which
samplecansurface
be collected
whichthrough
can be
the SNOMthrough
collected tip aperture.
the SNOM tip aperture.
Figure 15a–c show the AFM, c-SNOM, and SEM images, respectively, of the same copper
nanoparticle super lattice. Figure Figure 15d
15d shows
shows c-SNOM
c-SNOM scans z-direction for the two line sections,
scans in z-direction
A–A’
A–A’ and
and B–B’
B–B’ representing
representing superlattice
superlattice and
and disordered
disordered areas.
areas. The
The light fields displayed indicate that
section A–A’
A–A’ demonstrates
demonstrates evanescent
evanescent waveguiding
waveguiding properties
properties by by the strong intensity observed near
the surface with an an absence
absence of of destructive
destructive interference.
interference. Another scan along the section B–B’ with
disordered nanoparticles exhibits the expected intensity oscillation along the z-axis that indicates indicates
incoherent MieMie scattering
scattering from from randomly
randomly arrayed
arrayed nanoparticles
nanoparticles [60].
[60].
The integrated light light intensity
intensityprofiles
profilesextracted
extractedfromfromFigure
Figure15d 15dare
areshown
shown inin panel
panel e relative
e relative to
to
thethe distance
distance awayaway from
from the surface,z.z.Figure
thesurface, Figure15e
15eshows
showsan anexponential
exponentialdecay decay ofof light intensity is
observed
observed in inthe
theproximity
proximity of of
ordered nanoparticle
ordered arrays
nanoparticle (region
arrays A–A’)A–A’)
(region moving away from
moving awaythefrom
surface,
the
in agreement
surface, with thewith
in agreement evanescent wave decay
the evanescent waveprofile. By contrast
decay profile. the scattered
By contrast light intensity
the scattered from
light intensity
the
fromdisordered section
the disordered B–B’ B–B’
section shows multiple
shows oscillations.
multiple ThisThis
oscillations. effect arises
effect from
arises froma superposition
a superposition of
multipole
of multipoleandandincoherent
incoherent MieMie scattering
scattering[60].
[60].
Appl.
Appl. Sci. 2017, 7,
Sci. 2017, 7, 973
973 21
21 of
of 25
25

Figure 15. (a) AFM, (b) c-SNOM, and (c) SEM images obtained for the same area of a copper
Figure 15. (a)superlattice;
nanoparticle AFM, (b) c-SNOM,
(d) c-SNOMand scans
(c) SEM images
in the obtained
z-direction forfor the sections
cross same areaA–A’of and
a copper
B–B’
in panels a–c; (e) The integrated intensity shown in panel d identifies the exponentialB–B’
nanoparticle superlattice; (d) c-SNOM scans in the z-direction for cross sections A–A’ and in
decay
panels
of a–c; (e) Thewave
the evanescent integrated
moving intensity shown
away from theinsurface
panel dalong
identifies the exponential
the region decay of the
A–A’ representing an
evanescent wave moving away from the surface along the region A–A’ representing
ordered superlattice. Random interference patterns are observed for the randomly disordered area an ordered
superlattice.
B–B’; (f) LightRandom interference
scattering within thepatterns are observed
superlattices is coherentforas
the
therandomly disordered area
periodic nanoparticles actB–B’;
as a
(f) Light scattering within the superlattices is coherent as the periodic nanoparticles act as
waveguide; (g) Randomly distributed nanoparticles result in incoherent scattering and light absorption.a waveguide;
(g) Randomly
Reproduced withdistributed
permission nanoparticles result RSC
from [28], Copyright in incoherent scattering and light absorption.
Advances, 2015.
Reproduced with permission from [28], Copyright RSC Advances, 2015.

The underlying mechanism of the copper nanoparticle array waveguide begins with laser
The underlying mechanism of the copper nanoparticle array waveguide begins with laser light
light incident on the graphene at grazing incidence. In this case, the presence of the graphene
incident on the graphene at grazing incidence. In this case, the presence of the graphene layer
layer determines the polarization of the propagating light. Graphene is an optically anisotropic
determines the polarization of the propagating light. Graphene is an optically anisotropic material
material where the dielectric constant possesses a large in-plane imaginary part, while the out-of-plane
where the dielectric constant possesses a large in-plane imaginary part, while the out-of-plane
imaginary part is very close to zero [62]. The result is that for light propagating a grazing incidence
imaginary part is very close to zero [62]. The result is that for light propagating a grazing incidence to
to the graphene edge, the in plane polarization component becomes strongly attenuated, while the
the graphene edge, the in plane polarization component becomes strongly attenuated, while the out-of-
out-of-plane component will continue to propagate along the graphene surface without significant
plane component will continue to propagate along the graphene surface without significant attenuation.
attenuation. The nanoparticle superlattice offers a preferential direction for light propagation compared
The nanoparticle superlattice offers a preferential direction for light propagation compared to
to unmodified graphene, corresponding to the direction of parallel lines of copper nanoparticles.
unmodified graphene, corresponding to the direction of parallel lines of copper nanoparticles.
6. Conclusions
6. Conclusions
In conclusion, our review shows that advanced SNOM is a powerful imaging technique
with In conclusion,
immense our review
potential that has shows that advanced
so been SNOM
only partially is a powerful
realized. With theimaging
adventtechnique
of advancedwith
immense potential
nanofabrication that hasitsoisbeen
methods, nowonly partially
possible realized.designer
to produce With thec-SNOM
advent oftips
advanced nanofabrication
of varied composition
methods, it is now possible to produce designer c-SNOM tips of varied composition
with finely controlled aperture sizes from 100 nm to as small as 20 nm. Studies have shown that withSNOM
finely
controlled
is aperture
able to map sizes from
the complete 100 nm to as small
electromagnetic as 20ofnm.
near-field Studies have even
nanostructures, shown that SNOM
without is able
resorting to
to map the complete electromagnetic near-field of nanostructures, even without resorting to specialized
specialized tip designs. Access to this unique near-field information has significant potential to improve
tip design
the designs.andAccess to this unique
performance near-field information
of optoelectronic has significant
devices. Imaging near-fieldspotential to improve isthe
in three dimensions a
design and performance of optoelectronic devices. Imaging near-fields in three dimensions is a
natural extension on traditional 2D c-SNOM mapping to examine nanostructures, complementing
Appl. Sci. 2017, 7, 973 22 of 25

natural extension on traditional 2D c-SNOM mapping to examine nanostructures, complementing the

already robust list of complimentary techniques available including Raman, FTIR, and electromagnetic
field imaging.
Nanoparticles and nanostructures have the potential to revolutionize device architecture and
design by imparting new functionality to already established technologies. 3D SNOM is positioned to
encourage this revolution by providing the capability to fully characterize scattered and near-field light
from nanoparticles and nanostructures, and exploit them to improve device properties. Examination
of the near-field of metal nanoparticles using 3D SNOM has been used to enhance the performance
of organic BHJ solar cells through an increased understanding on the forward scattered light field.
Efficient control of scattered light in solar cells enabled by 3D SNOM could lead to increased PCE
without significant changes to existing solar cell architectures. 3D SNOM has also been shown to have
the capability of mapping all components of electric and magnetic fields above PhCW structures using
standard circular aperture tips.
3D SNOM is also not limited to mapping of light and electromagnetic near-fields. The sub
wavelength resolution of SNOM can be combined with other techniques not covered in this article-such
as thermoreflectance-to enhance the resolution beyond the diffraction limit and obtain the nanoscale
thermal conductivity. Synergy with an AFM system also allows SNOM to be easily coupled with
other nanoscale force microscopies such as Kelvin probe force microscopy or conducting probe AFM.
Multiple SNOM systems can be coupled together to simultaneously inject and collect light from
nanostructures [58]. Time resolved studies are also possible with switching or chopping of external
light sources to examine temporal properties of nanostructured surfaces. Modifications to AFM More
exotic modifications can be considered. SNOM has been shown to be well suited for investigation of
biological systems where non-destructive and contactless methods are in high demand for nanoscale
imaging of live cells [57]. 3D SNOM is envisaged to lead to breakthroughs in the study of biological
systems with nanoscale imaging of live cells, as well as improved design and operation of nanoscale
light management devices. 3D SNOM is well positioned to augment the study of nanoscale properties
of materials, with a bright future ahead for sub-wavelength resolution imaging.

Acknowledgments: P.B. acknowledges a MITACS Accelerate Postdoctoral Fellowship. G.F. acknowledges a

Canada Research Chair in carbon-based nanomaterials and Nano-optoelectronics. The authors would like
to thank Teeno Ouyang, Jaewoo Park and Reg J. Bauld for some of the experiments that led to the results
discussed here, and for fruitful discussions. Funding from the Canada Foundation for Innovation (grant No.
212442) and the Discovery Grant program of the Natural Sciences and Engineering Research Council of Canada
(RGPIN-2015-06004) are also gratefully acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Weisenburger, S.; Sandoghdar, V. Light microscopy: An ongoing contemporary revolution. Contemp. Phys.
2015, 56, 123–143. [CrossRef]
2. Hell, S.W. Toward fluorescence nanoscopy. Nat. Biotechnol. 2003, 21, 1347–1355. [CrossRef] [PubMed]
3. Sarunic, M.V.; Weinberg, S.; Izatt, J.A. Full-field swept-source phase microscopy. Opt. Lett. 2006, 31,
1462–1464. [CrossRef] [PubMed]
4. Dubois, A.; Vabre, L.; Boccara, A.-C.; Beaurepaire, E. High-resolution full-field optical coherence tomography
with a Linnik microscope. Appl. Opt. 2002, 41, 805–812. [CrossRef] [PubMed]
5. Shirazi, M.F.; Kim, P.; Jeon, M.; Kim, J. Full-field optical coherence tomography using galvo filter-based
wavelength swept laser. Sensors 2016, 16, 1933. [CrossRef] [PubMed]
6. Huang, B.; Wang, W.; Bates, M.; Zhuang, X. Three-dimensional super-resolution imaging by stochastic
optical reconstruction microscopy. Science 2008, 319, 810–813. [CrossRef] [PubMed]
7. Huang, B.; Jones, S.A.; Brandenburg, B.; Zhuang, X. Whole-cell 3D STORM reveals interactions between
cellular structures with nanometer-scale resolution. Nat. Methods 2008, 5, 1047–1052. [CrossRef] [PubMed]
8. Rotenberg, N.; Kuipers, L. Mapping nanoscale light fields. Nat. Photonics 2014, 8, 919–926. [CrossRef]
Appl. Sci. 2017, 7, 973 23 of 25

9. Neumann, L.; Pang, Y.; Houyou, A.; Juan, M.L.; Gordon, R.; van Hulst, N.F. Extraordinary optical
transmission brightens near-field fiber probe. Nano Lett. 2011, 11, 355–360. [CrossRef] [PubMed]
10. Ogletree, D.F.; Schuck, P.J.; Weber-Bargioni, A.F.; Borys, N.J.; Aloni, S.; Bao, W.; Barja, S.; Lee, J.; Melli, M.;
Munechika, K.; et al. Revealing optical properties of reduced-dimensionality materials at relevant length
scales. Adv. Mater. 2015, 27, 5693–5719. [CrossRef] [PubMed]
11. Denkova, D.; Verellen, N.; Silhanek, A.V.; Valev, V.; Dorpe, P.V.; Moshchalkov, V.V. Mapping magnetic
near-field distributions of plasmonic nanoantennas. ACS Nano 2013, 7, 3168–3176. [CrossRef] [PubMed]
12. Novotny, L.; Pohl, D.W.; Hecht, B. Scanning near-field optical probe with ultrasmall spot size. Opt. Lett.
1995, 20, 970. [CrossRef] [PubMed]
13. Bek, A.; Vogelgesang, R.; Kern, K. Apertureless scanning near-field optical microscope with sub-10 nm
resolution. Rev. Sci. Instrum. 2006, 77, 043703. [CrossRef]
14. Zenhausern, F.; O’Boyle, M.P.; Wickramasinghe, H.K. Apertureless near-field optical microscope. Appl. Phys.
Lett. 1994, 65, 1623. [CrossRef]
15. Hecht, B.; Bielefeldt, H.; Inouye, Y.; Pohl, D.; Novotny, L. Facts and artifacts in near-field optical microscopy.
J. Appl. Phys. 1997, 81, 2492. [CrossRef]
16. Lereu, A.; Passian, A.; Dumas, P. Near-field optical microscopy: A brief review. Int. J. Nanotechnol. 2012, 9,
3–7. [CrossRef]
17. Zhang, W.; Fang, Z.; Zhu, X. Near-field Raman spectroscopy with aperture tips. Chem. Rev. 2017, 117,
5095–5109. [CrossRef] [PubMed]
18. Li, J.F.; Huang, Y.F.; Ding, Y.; Yang, Z.L.; Li, S.B.; Zhou, X.S.; Fan, F.R.; Zhang, W.; Zhou, Z.Y.; Wu, D.Y.; et al.
Shell-isolated nanoparticle-enhanced Raman spectroscopy. Nature 2010, 464, 392–395. [CrossRef] [PubMed]
19. Kulzer, F.; Orrit, M. Single-molecule optics. Annu. Rev. Phys. Chem. 2004, 55, 585. [CrossRef] [PubMed]
20. Baschè, T.; Moerner, W.E.; Orrit, M.; Wild, U.P. Single-Molecule Optical Detection, Imaging and Spectroscopy;
VCH: Weinheim, Germany, 1997. [CrossRef]
21. Tsien, R.Y.; Waggoner, A. Fluorophores for confocal microscopy: Photophysics and photochemistry.
In Handbook of Biological Confocal Microscopy; Springer: New York, NY, USA, 2006; pp. 338–352.
22. Tsien, R.Y. The green fluorescent protein. Annu. Rev. Biochem. 1998, 67, 509. [CrossRef] [PubMed]
23. Stevension, R.; Milner, R.G.; Richards, D.; Arias, A.C.; Mackenzie, J.D.; Halls, J.J.M.; Friend, R.H.; Kang, D.-J.;
Blamire, M. Fluorescence scanning near-field optical microscopy of polyfluorene composite. J. Microsc. 2001,
202, 433–438. [CrossRef]
24. Müller-Zülow, B.; Kämmer, S.; Gehring, S.; Reineke, F. Fluorescence and luminescence testing of electronical
devices with SNOM. Microelectron. Eng. 1996, 31, 163–168. [CrossRef]
25. Freudiger, C.W.; Min, W.; Saar, B.G.; Lu, S.; Holtom, G.R.; He, C.; Tsai, J.C.; Kang, J.X.; Xie, X.S. Label-free
biomedical imaging with high sensitivity by stimulated Raman scattering microscopy. Science 2008, 322,
1857. [CrossRef] [PubMed]
26. Pashaee, F.; Sharifi, F.; Fanchini, G.; Lagugné-Labarthet, F. Tip-enhanced Raman spectroscopy of
graphene-like and graphitic platelets on ultraflat gold nanoplates. Phys. Chem. Chem. Phys. 2015, 17, 21315.
[CrossRef] [PubMed]
27. Ayas, S.; Cinar, G.; Ozkan, A.D.; Soran, Z.; Ekiz, O.; Kocaay, D.; Tomak, A.; Toren, P.; Kaya, Y.; Tunc, I.;
et al. Label-free nanometer-resolution imaging of biological architectures through surface enhanced Raman
scattering. Sci. Rep. 2013, 3, 2624. [CrossRef] [PubMed]
28. Ouyang, T.; Akbari-Sharbaf, A.; Park, J.; Bauld, R.; Cottam, M.G.; Fanchini, G. Self-assembled metallic
nanoparticle superlattices on large-area graphene thin films: Growth and evanescent waveguiding properties.
RSC Adv. 2015, 5, 98814–98821. [CrossRef]
29. Le Feber, B.; Rotenberg, N.; Beggs, D.M.; Kuipers, L. Simultaneous measurement of nanoscale electric and
magnetic optical fields. Nat. Photonics 2014, 8, 43–46. [CrossRef]
30. Rotenberg, N.; Krijger, T.L.; le Feber, B.; Spasenović, M.; Javier García de Abajo, F.; Kuipers, L. Magnetic and
electric response of single subwavelength holes. Phys. Rev. B 2013, 88, 241408(R). [CrossRef]
31. Rotenberg, N.; Spasenović, M.; Krijger, T.L.; le Feber, B.; de Abajo, F.G.; Kuipers, L. Plasmon scattering from
single subwavelength holes. Phys. Rev. Lett. 2012, 108, 127402. [CrossRef] [PubMed]
32. Burresi, M.; van Oosten, D.; Kampfrath, T.; Schoenmaker, H.; Heideman, R.; Leinse, A.; Kuipers, L. Probing
the magnetic field of light at optical frequencies. Science 2009, 326, 550–553. [CrossRef] [PubMed]
Appl. Sci. 2017, 7, 973 24 of 25

33. Denkova, D.; Verellen, N.; Silhanek, A.V.; van Dorpe, P.; Moshchalkov, V.V. Lateral magnetic near-field
imaging of plasmonic nanoantennas with increasing complexity. Small 2014, 10, 1959–1966. [CrossRef]
[PubMed]
34. Kihm, H.W.; Kim, J.; Koo, S.; Ahn, J.; Ahn, K.; Lee, K.; Park, N.; Kim, D.-S. Optical magnetic field mapping
using a subwavelength aperture. Opt. Exp. 2013, 21, 5625–5633. [CrossRef] [PubMed]
35. Schnell, M.; García-Etxarri, A.; Alkorta, J.; Aizpurua, J.; Hillenbrand, R. Phase-resolved mapping of the
near-field vector and polarization state in nanoscale antenna gaps. Nano Lett. 2010, 10, 3524–3528. [CrossRef]
[PubMed]
36. Koenderink, A.F.; Kafesaki, M.; Buchler, B.C.; Sandoghdar, V. Controlling the resonance of a photonic crystal
microcavity by a near-field probe. Phys. Rev. Lett. 2005, 95, 153904. [CrossRef] [PubMed]
37. Lalouat, L.; Cluzel, B.; Velha, P.; Picard, E.; Peyrade, D.; Hugonin, J.P.; Lalanne, P.; Hadji, E.; de Fornel, F.
Near-field interactions between a subwavelength tip and a small-volume photonic-crystal nanocavity.
Phys. Rev. B 2007, 76, 041102(R). [CrossRef]
38. Chen, J.; Badioli, M.; Alonso-González, P.; Thongrattanasiri, S.; Huth, F.; Osmond, J.; Spasenović, M.;
Centeno, A.; Pesquera, A.; Godignon, P.; et al. Optical nano-imaging of gate-tunable graphene plasmons.
Nature 2012, 487, 77–81. [CrossRef] [PubMed]
39. Chorsi, H.T.; Zhang, J.X.J. Apertureless near-field scanning probes based on graphene plasmonics.
IEEE Photonics J. 2017, 9, 4800207. [CrossRef]
40. Kauranen, M.; Zayats, A.V. Nonlinear plasmonics. Nat. Photonics 2012, 6, 737–748. [CrossRef]
41. Ikeda, S.; Cai, Y.; Meng, Q.; Yokoyama, T.; Shinozaki, K.; Komatsu, T.; Ishibashi, T. Imaging of localized
surface plasmon by apertureless scanning near-field optical microscopy. Sens. Mater. 2015, 27, 985–991.
42. Amenabar, I.; Poly, S.; Nuansing, W.; Hubrich, E.H.; Govyadinov, A.A.; Huth, F.; Krutokhvostov, R.; Zhang, L.;
Knez, M.; Heberle, J.; et al. Structural analysis and mapping of individual protein complexes by infrared
nanospectroscopy. Nat. Commun. 2013, 4, 2890. [CrossRef] [PubMed]
43. Huth, F.; Schnell, M.; Wittborn, J.; Ocelic, N.; Hillenbrand, R. Infrared-spectroscopic nanoimaging with a
thermal source. Nat. Mater. 2011, 10, 352–356. [CrossRef] [PubMed]
44. Jones, A.C.; Raschke, M.B. Thermal infrared near-field spectroscopy. Nano Lett. 2012, 12, 1475–1481.
[CrossRef] [PubMed]
45. Westermeier, C.; Cernescu, A.; Amarie, S.; Liewald, C.; Keilmann, F.; Nickel, B. Sub-micron phase coexistence
in small-molecule organic thin films revealed by infrared nano-imaging. Nat. Commun. 2014, 5, 4101.
[CrossRef] [PubMed]
46. Umeda, N.; Hayashi, Y.; Nagai, K.; Takayanagi, A. Scanning wiener-fringe microscope with an optical fiber
tip. Appl. Opt. 1992, 31, 4515–4518. [CrossRef] [PubMed]
47. Bacsa, W.; Levine, B.; Caumont, M. Local optical field variation in the neighborhood of a semiconductor
micrograting. J. Opt. Soc. Am. B 2006, 23, 893–896. [CrossRef]
48. Ezugwu, S.; Yea, H.; Fanchini, G. Three-dimensional scanning near-field optical microscopy (3D-SNOM)
imaging of random arrays of copper nanoparticles: Implications for plasmonic solar cell enhancement.
Nanoscale 2015, 7, 252–260. [CrossRef] [PubMed]
49. Martinez-Marrades, A.; Greusard, L.; de Wilde, Y.; Bardou, N.; Collin, S.; Guillon, M.; Tessier, G.
Characterization of plasmonic nano antennas by holographic microscopy and scanning near-field microscopy.
Opt. Commun. 2016, 359, 455–459. [CrossRef]
50. Li, Y.; Zhou, N.; Raman, A.; Xu, X. Three-dimensional mapping of optical near-field with scattering SNOM.
Opt. Exp. 2015, 23, 18730–18735. [CrossRef] [PubMed]
51. Guo, R.; Kinzel, E.C.; Li, Y.; Uppuluri, S.M.; Raman, A.; Xu, X. Three-dimensional mapping of optical
near-field of a nanoscale bowtie antenna. Opt. Exp. 2010, 18, 4961–4971. [CrossRef] [PubMed]
52. Zhou, N.; Li, Y.; Xu, X. Resolving near-field from high order signals of scattering near-field scanning optical
microscopy. Opt. Exp. 2014, 22, 18715–18723. [CrossRef] [PubMed]
53. Olmon, R.L.; Rang, M.; Krenz, P.M.; Lail, B.A.; Saraf, L.V.; Boreman, G.L.; Raschke, M.B. Determination of
electric-field, magnetic-field, and electric-current distributions of infrared optical antennas: A near-field
optical vector network analyzer. Phys. Rev. Lett. 2010, 105, 167403. [CrossRef] [PubMed]
54. Bauld, R.; Hesari, M.; Workentin, M.S.; Fanchini, G. Thermal stability of Au25 − Molecular precursors and
nucleation of gold nanoparticles in thermosetting polyimide thin films. Appl. Phys. Lett. 2012, 101, 243114.
[CrossRef]
Appl. Sci. 2017, 7, 973 25 of 25

55. Costantini, D.; Greusard, L.; Bousseksou, A.; Rungsawang, R.; Zhang, T.P.; Callard, S.; Decobert, J.; Lelarge, F.;
Duan, G.-H.; de Wilde, Y.; et al. In situ generation of surface plasmon polaritons using a near-infrared laser
diode. Nano Lett. 2012, 12, 4693–4697. [CrossRef] [PubMed]
56. Liu, M.; Wagner, M.; Zhang, J.; McLeod, A.; Kittiwatanakul, S.; Fei, Z.; Abreu, E.; Goldflam, M.;
Sternbach, A.J.; Dai, S.; et al. Symmetry breaking and geometric confinement in VO2 : Results from a
threedimensional infrared nano-imaging. Appl. Phys. Lett. 2014, 104, 121905. [CrossRef]
57. Bulat, K.; Rygula, A.; Szafraniec, E.; Ozaki, Y.; Baranska, M. Live endothelial cells imaged by scanning
near-field optical microscopy (SNOM): Capabilities and challenges. J. Biophotonics 2017, 10, 928–938.
[CrossRef] [PubMed]
58. Klein, A.E.; Janunts, N.; Schmidt, S.; Hasan, S.B.; Etrich, C.; Fasold, S.; Kaiser, T.; Rockstuhle, C.; Pertsch, T.
Dual-SNOM investigations of multimode interference in plasmonic strip waveguides. Nanoscale 2017, 9,
6695–6702. [CrossRef] [PubMed]
59. Garcia, M.A. Surface plasmons in metallic nanoparticles: Fundamentals and applications. J. Phys. D
Appl. Phys. 2011, 44, 283001. [CrossRef]
60. Hecht, B.; Bielefeldt, H.; Novotny, L.; Inouye, Y.; Pohl, D.W. Local excitation, scattering, and interference of
surface plasmons. Phys. Rev. Lett. 1996, 77, 1889. [CrossRef] [PubMed]
61. Kim, H.J.; Ji, W.S.; O, B.-h.; Park, S.; Lee, E.-H.; Lee, S.G. Characterization of a focusing waveguide grating
coupler using a bloch-wave analysis-based local linear grating model and near-field scanning optical
microscope. J. Korean Phys. Soc. 2005, 46, 1013–1019.
62. Cheon, S.; Kihm, K.; Kim, H.; Lim, G.; Park, J.S.; Lee, J.S. How to reliably determine the complex refractive
index (RI) of graphene by using two independent measurement constraints. Sci. Rep. 2014, 4, 6364. [CrossRef]
[PubMed]

© 2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).